Structure for pattern formation, method for pattern formation, and application thereof

ABSTRACT

A structure for pattern formation adapted for optically forming a pattern, characterized by comprising: a photocatalyst-containing layer provided on a substrate, the photocatalyst-containing layer containing a material of which the wettability is variable through photocatalytic action upon pattern-wise exposure.

TECHNICAL FIELD

The present invention relates to a novel structure for pattern formationusable for various applications, preferably a structure for patternformation utilizing a variation in wettability and a method for patternformation, and application thereof to printing, color filters, lensesand the like.

BACKGROUND ART

Prior art techniques relevant to first invention A will be described.

Structures for pattern formation comprising a substrate having on itssurface areas different from neighboring areas in wettability, forexample, by liquids have been used in various technical fields. Forexample, in structures for pattern formation used in printing ofdesigns, images, letters and the like, a pattern is provided which, upontransfer of a printing ink, receives or repels the ink. In some cases,this pattern is in the form of a patterned layer or a transferred layerformed on the structure for pattern formation according to a variationin wettability.

This will described by taking printing as an example. In plates forlithography, i.e., a kind of printing method, printing ink-receptivelipophilic areas and printing ink-unreceptive areas are provided on aflat plate. In use, an ink image to be printed is formed on thelipophilic areas and then transferred and printed onto paper or thelike.

In this printing, a pattern of letters, figures or the like is formed onan original plate for a printing plate to prepare a printing plate thatis then mounted on a printing machine. A large number of proposals havebeen made on original plates for printing plates that are used in offsetprinting which is representative lithography.

Plates for offset printing may be produced by a method wherein theoriginal plate for a printing plate is exposed through a mask with apattern drawn thereon followed by development, and a method wherein theoriginal plate for a printing plate is directly exposed byelectrophotography to prepare a printing plate. The original plate foran electrophotographic offset printing plate is prepared by a methodwhich comprises the steps of: providing a photoconductive layer composedmainly of photoconductive particles of zinc oxide or the like and abinder resin on a conductive substrate to form a photoreceptor; exposingthe photoreceptor by electrophotography to form a highly lipophilicimage on the surface of the photoreceptor; and subsequently treating thephotoreceptor with a desensitizing liquid to hydrophilify nonimage areasto prepare an original plate for offset printing. High critical surfacetension areas are immersed in water or the like and is consequentlylipophobified, and a printing ink is received by the lipophilic imageareas followed by transfer onto paper or the like.

An original plate for waterless lithography has also been used wherein,instead of the immersion in water to form lipophobic areas, highlylipophobic areas are formed without relying upon immersion in water orthe like to form ink-receptive areas and ink-unreceptive areas.

Further, a method for producing an original plate for lithography usinga heat mode recording material has been proposed which can realize theformation of highly ink-receptive areas and ink-repellent areas by laserbeam irradiation. Heat mode recording materials can eliminate the needto provide the step of development and the like, and advantageouslyenables printing plates to be produced simply by forming an image usinga laser beam. They, however, suffer from problems associated with theregulation of laser beam intensity, the disposal of residues of solidmaterials denatured by the laser, the plate wear and the like.

Furthermore, photolithography is known as a method for forming a highdefinition pattern. In this method, for example, a photoresist layercoated onto a substrate is pattern-wise exposed, and the exposedphotoresist is developed, followed by etching. Alternatively, afunctional material is used in a photoresist, and the photoresist isexposed to directly form a contemplated pattern.

The formation of a high definition pattern by photolithography has beenused for the formation of color patterns in color filters for liquidcrystal displays and the like, the formation of microlenses, theproduction of high definition electric circuit boards, the production ofchromium masks for pattern-wise exposure and other applications. Inthese methods, however, in addition to the use of the photoresist,development using a liquid developing solution or etching should becarried out after the exposure. This poses problems including thenecessity of treating waste liquid. Further, use of a functionalmaterial as the photoresist disadvantageously raises problems includingdeterioration of the photoresist by an alkaline liquid or the like usedin the development.

Formation of a high definition pattern for color filters or the like byprinting or the like has also been carried out. Patterns formed byprinting suffer from problems of positional accuracy and the like, and,hence, in this method, it is difficult to form high definition patterns.

In order to solve these problems, the present inventors have alreadyproposed, in Japanese Patent Application No. 214845/1997, a structurefor pattern formation and a method for pattern formation wherein amaterial, of which the wettability is variable through photocatalyticaction, is used to form a pattern. According to the present invention,in the structure and method for pattern formation using a photocatalyst,structure and method for pattern formation having better properties areprovided.

It is an object of the first invention A to provide a novel structurefor pattern formation and a method for pattern formation. It is anotherobject of the first invention A to provide a novel original plate for aprinting plate that can solve the problems of the conventional originalplates for printing plates. It is a further object of the firstinvention A to provide a structure for pattern formation and a methodfor pattern formation that can be used to provide functional elementshaving excellent properties.

Prior art techniques relevant to second invention B will be described.

In liquid crystal display devices (LCDs), color filters are used in bothactive matrix system and simple matrix system in order to cope with anincreasing demand for color display in recent years. For example, inliquid crystal displays of active matrix system using a thin filmtransistor (TFT), the color filter has color patterns of the threeprimary colors of red (R), green (G), and blue (B), and electrodescorresponding respectively to pixels of R, G, and B are turned on or offto permit a liquid crystal to function as a shutter, whereby lightpasses through pixels of R, G, and B to perform color display. In thecase of color mixing, liquid crystal shutters corresponding to two ormore pixels are opened to mix colors together so that, on the principleof additive color process, a viewer sees a different color on theretina.

Examples of methods for producing conventional color filters include adyeing method which comprises coating a dyeing substrate onto atransparent substrate, exposing the coated substrate through aphotomask, conducting development to form a pattern, and dyeing thepattern to form a colored layer, a pigment dispersion method whichcomprises previously dispersing a color pigment in a photosensitiveresist layer provided on a transparent substrate, exposing the resistlayer through a photomask, and conducting development to form a coloredlayer, a printing method which comprises printing colored layers usingprinting inks onto a transparent substrate, and an electrodepositionmethod which comprises forming a transparent electrode pattern on atransparent substrate and repeating, three times for R, G, and B, theenergization of the transparent electrode pattern in an electrode liquidof a predetermined color to electrodeposit the color, thereby formingpatterns of the colors.

In the conventional dyeing method and pigment dispersion method,however, material loss cannot be avoided in the step of coating thetransparent substrate by spin coating or the like, and, further, thestep of development and the step of washing are necessary for theformation of a pattern of each color. This makes it difficult to improvethe efficiency of use of the material and to simplify the process andhence hinders a reduction in production cost. On the other hand, for theprinting method, the formation of high definition patterns is difficult,and, for the electrodeposition method, the shape of patterns formable bythe electrodeposition is limited.

In order to eliminate the above problems, a process for producing acolor filter by ink-jet system has been developed. This process,however, is still unsatisfactory for solution to the problems.

The second invention B has been made under these circumstances. It is anobject of the present invention to provide a color filter having highdefinition and free from defects such as dropouts and to provide aproduction process of a color filter that is excellent in efficiency ofuse of the material and includes neither the step of development nor thestep of washing, that is, is simple in process.

Prior art techniques relevant to the third invention will be described.

Among lenses used in the art, particularly a microlens or a microlensarray comprising orderly arranged microlenses has been utilized in fineoptics and other fields. For example, there is an ever-increasing demandfor use of the microlens or the microlens array as componentsconstituting liquid crystal displays and as components adjacent tocharge coupled solid-state image pick-up device (CCD) used in videocameras and the like.

For the production of microlenses, for example, Japanese PatentLaid-Open Nos. 21901/1991 and 164904/1993 disclose a production processwhich comprises forming a transparent heat deformable resin pattern byetching through a mask and heat deforming the heat deformable resinpattern to form a microlens. In this process, however, the formation offine lenses is difficult because the direction of etching is isotropic.Further, the regulation of the focal length of the lens is limited, andthe process is complicate.

Japanese Patent Laid-Open No. 165932/1990 discloses another conventionalprocess for producing a microlens which comprises ejecting droplets of acomposition for a lens onto a transparent substrate and curing thedeposited droplets to form a microlens array. In this process, however,the shape of the lens is restricted by the contact angle between thetransparent substrate and the composition for the lens, making itdifficult to regulate the focal length. Further, in order to provide aspecific contact angle, a composition for a lens having a specificsurface tension should be selected. This narrows the range of selectablematerials. Furthermore, the shape of the contact face is limited to acircular one, and a contact face having a polygonal pattern cannot beprovided. A further problem is that enhancing the radius of curvaturerequires for the substrate to repel the composition for a lens. Thisdeteriorates the adhesion.

Further, Japanese Patent Laid-Open No. 206429/1993 proposes a methodwherein functions of a microlens array and a color filter arraycomprising a plurality of stacked color filters can be realized by asingle color microlens array layer.

The color microlens array may be produced, for example, by a processdescribed in Japanese Patent Laid-Open No. 206429/1993. This processcomprises forming a color filter array by photolithography, formingmicrolens dies on respective color filters, and transferring the diesonto the color filter array by isotropic etching to form a microlens ofthe color filter array. Further, Japanese Patent Application No.201793/1996 discloses a production process which comprises formingrecesses in a lens form in a glass substrate by using a photoresist andglass etching and filing colored lens materials into respective colorportions. In the former production process, however, the process is verycomplicate, and, in the latter production process, a lens is formed inrecesses of a glass substrate, posing problems including that it is verydifficult to control the step of etching and the effect of lens cannotbe attained without increasing the refractive index of the lens formingmaterial.

The third invention C solves the above problems. It is an object of thepresent invention to provide a process for producing a lens in a simplemanner, particularly a production process that can produce finemicrolenses and a microlens array with good positional accuracy andenables the focal length of microlenses to be easily altered, andlenses, microlenses, and a microlens array produced by the productionprocess.

Prior art techniques relevant to the fourth invention D will bedescribed.

In plates for lithography, i.e., a kind of printing method, printingink-receptive lipophilic areas and printing ink-unreceptive areas areprovided on a flat plate. In use, an ink image to be printed is formedon the lipophilic areas, and the image is then transferred and printedonto paper or the like.

In this printing, various original plates for printing plates are used.After formation of a pattern of letters, figures or the like on plates,the plates are used for printing. A large number of proposals have beenmade on original plates for printing plates used in offset printing,representative lithographic plates. Among them, original plates foroffset printing plates directly prepared by electrophotography have beenwidely used in the art. The original plate for an electrophotographicoffset printing plate is prepared by a method which comprises the stepsof: providing a photoconductive layer composed mainly of photoconductiveparticles of zinc oxide or the like and a binder resin on a conductivesubstrate to form a photoreceptor; exposing the photoreceptor byelectrophotography to form a highly lipophilic image on the surface ofthe photoreceptor; and subsequently treating the photoreceptor with adesensitizing liquid to hydrophilify nonimage areas to prepare anoriginal plate for offset printing. High critical surface tension areasare immersed in water or the like and is consequently lipophobified, anda printing ink is received by the lipophilic image areas followed bytransfer onto paper or the like.

An original plate for waterless lithography has also been used wherein,instead of the immersion in water to form lipophobic areas, highlylipophobic areas are formed without relying upon immersion in water orthe like to form ink-receptive areas and ink-unreceptive areas.

Further, a method for producing an original plate for lithography usinga heat mode recording material has been proposed which can realize theformation of highly ink-receptive areas and ink-repellent areas by laserbeam irradiation.

Heat mode recording materials can eliminate the need to provide the stepof development and the like, and advantageously enables an originalprinting plate to be produced simply by forming an image using a laserbeam. They, however, suffer from problems associated with the regulationof laser beam intensity, the disposal of residues of solid materialsdenatured by the laser, the plate wear and the like.

In order to solve these problems, the present inventors have alreadyproposed, in Japanese Patent Application No. 214845/1997, a structurefor pattern formation and a method for pattern formation wherein amaterial of which the wettability is variable through photocatalyticaction is used to form a pattern. In this connection, the production ofpress plates having excellent properties by utilizing original platesfor printing plates using the pattern forming structure using aphotocatalyst has been desired in the art.

It is an object of the fourth invention D to provide a press platehaving excellent properties by utilizing an original plate for aprinting plate using a structure for pattern formation prepared throughphotocatalytic action.

DISCLOSURE OF THE INVENTION

Re: First Invention A

The present invention provides a structure for pattern formation adaptedfor optically forming a pattern, the structure comprising aphotocatalyst-containing layer provided on a substrate, thephotocatalyst-containing layer containing a material of which thewettability is variable through photocatalytic action upon pattern-wiseexposure.

The present invention also provides a structure for pattern formationadapted for optically forming a pattern, the structure comprising: asubstrate; a photocatalyst-containing layer provided on the substrate;and, provided on the photocatalyst-containing layer, a layer that isdecomposable and removable through photocatalytic action uponpattern-wise exposure.

The present invention further provides a structure for pattern formationadapted for optically forming a pattern, the structure comprising: asubstrate; a photocatalyst-containing layer provided on the substrate;and, provided on the photocatalyst-containing layer, a layer containinga material of which the wettability is variable through photocatalyticaction upon pattern-wise exposure.

The present invention further provides a structure for pattern formationadapted for optically forming a pattern, the structure comprising acomposition layer, the composition layer comprising a photocatalyst, amaterial decomposable through photocatalytic action upon pattern-wiseexposure, and a binder.

In the above structure for pattern formation, thephotocatalyst-containing layer may contain a compound having siloxanebonds.

In the above structure for pattern formation, thephotocatalyst-containing layer may contain silicone.

In the above structure for pattern formation, fluoroalkyl groups may bebonded to silicon atoms in the silicone.

In the above structure for pattern formation, the silicone may have beenprepared from a composition containing an organoalkoxysilane.

In the above structure for pattern formation, the silicone may have beenprepared from a composition containing a reactive silicone compound.

In the above structure for pattern formation, the pattern formingstructure may be an original plate for a printing plate.

The present invention further provides a method for pattern formationadapted for optically forming a pattern comprising exposing pattern-wise

a structure for pattern formation comprising: a substrate; aphotocatalyst-containing layer provided on the substrate, thephotocatalyst-containing layer containing a material of which thewettability is variable through photocatalytic action,

a structure for pattern formation comprising: a substrate; aphotocatalyst-containing layer provided on the substrate; and, providedon the photocatalyst-containing layer, a layer containing a material ofwhich the wettability is variable through photocatalytic action,

a structure for pattern formation comprising: a substrate; aphotocatalyst-containing layer provided on the substrate; and, providedon the photocatalyst-containing layer, a layer that, upon pattern-wiseexposure, is decomposable and removable through photocatalytic action,or

a structure for pattern formation comprising: a substrate; and acomposition layer provided on the substrate, the composition layercomprising a photocatalyst, a material decomposable throughphotocatalytic action upon pattern-wise exposure, and a binder,

to vary the wettability of the surface of the structure throughphotocatalytic action.

In the above method for pattern formation, the pattern-wise exposure ofthe photocatalyst-containing layer may be carried out by light beamexposure.

In the above method for pattern formation, the pattern-wise exposure ofthe photocatalyst-containing layer may be carried out by exposurethrough a photomask.

In the above method for pattern formation, the pattern-wise exposure ofthe photocatalyst-containing layer may be carried out while heating thestructure for pattern formation.

The present invention further provides an element characterized bycomprising: a substrate; the above structure for pattern formationprovided on the substrate; and a functional layer provided on thestructure for pattern formation in its areas corresponding to a pattern,of the structure for pattern formation, obtained by the abovepattern-wise exposure.

The present invention further provides an element produced bytransferring a functional layer onto another substrate, the functionallayer being provided on a structure for pattern formation in its areascorresponding to a pattern, of the structure for pattern formation,obtained by the above pattern-wise exposure.

The present invention further relates to a process for producing anelement, comprising the steps of: providing the above structure forpattern formation on a substrate; and forming a functional layerprovided on the structure for pattern formation in its areascorresponding to a pattern, of the structure for pattern formation,obtained by the above pattern-wise exposure.

The present invention further relates to a process for producing anelement, comprising the step of transferring a functional layer ontoanother substrate, the functional layer being provided on a structurefor pattern formation in its areas corresponding to a pattern, of thestructure for pattern formation, obtained by the above pattern-wiseexposure, whereby the functional layer is formed on the anothersubstrate.

The above process for producing an element may comprise the steps of:forming a composition for a functional layer onto the whole surface of astructure for pattern formation; and forming a patterned functionallayer on the structure for pattern formation only in itswettability-varied exposed areas by utilizing the repellency ofunexposed areas.

The above process for producing an element may comprise the steps of:forming a composition for a functional layer onto the whole surface of astructure for pattern formation; and removing the functional layer inits unexposed areas to form a patterned functional layer.

The above process for producing an element may comprise the steps of:forming a composition for a functional layer onto the whole surface of astructure for pattern formation; and forming a patterned functionallayer on the structure for pattern formation only in itswettability-varied exposed areas by utilizing the repellency ofunexposed areas.

The above process for producing an element may comprise the steps of:forming a composition for a functional layer onto the whole surface of astructure for pattern formation; and removing the functional layer inits unexposed areas to form a patterned functional layer.

In the above process for producing an element, the functional layer maybe formed on the structure for pattern formation by coating acomposition for a functional layer.

In the above process for producing an element, the functional layer maybe formed on the structure for pattern formation by ejecting acomposition for a functional layer through a nozzle.

In the above process for producing an element the functional layer maybe formed on the structure for pattern formation by thermal or pressuretransfer from a film coated with a composition for a functional layer.

In the above process for producing an element, the functional layer maybe formed on the structure for pattern formation by film formationutilizing vacuum.

In the above process for producing an element, the functional layer maybe formed on the structure for pattern formation by film formationutilizing electroless plating.

Re: Second Invention B

In order to attain the above object, the present invention provides acolor filter comprising: a transparent substrate; a colored layerprovided on the transparent substrate, the colored layer comprising aplurality of colors formed in a predetermined pattern; and a lightshielding layer located at each boundary region between two adjacentcolored layers, at least one of the colored layer and the lightshielding layer having been formed on the transparent substrate througha wettability-variable component layer in its areas having specificwettability.

Further, the present invention provides a color filter comprising: atransparent substrate; a wettability-variable component layer providedon the transparent substrate; a colored layer of a plurality of colorsprovided in a predetermined pattern on the wettability-variablecomponent layer in its areas having specific wettability; and a lightshielding layer located at each boundary region between two adjacentcolored layers.

Further, the present invention provides a color filter comprising: atransparent substrate provided with a light shielding layer in apredetermined pattern; a wettability-variable component layer providedon the transparent substrate so as to cover the light shielding layer;and a colored layer of a plurality of colors provided in a predeterminedpattern on the wettability-variable component layer in its areas havingspecific wettability, the light shielding layer being located at eachboundary region between two adjacent colored layers.

Further, the present invention provides a color filter comprising: atransparent substrate provided with a light shielding layer in apredetermined pattern; laminates, in number of desired colors, put onthe transparent substrate so as to cover the light shielding layer, thelaminates each comprising a wettability-variable component layer and acolored layer provided in a predetermined pattern on thewettability-varied component layer in its areas having specificwettability, the light shielding layer being located at each boundaryregion between two adjacent colored layers.

Further, the present invention provides a color filter comprising: atransparent substrate; a wettability-variable component layer providedon the transparent substrate; a light shielding layer provided in apredetermined pattern on the wettability-variable component layer in itsareas having specific wettability; laminates, in number of desiredcolors, put on the wettability-variable component layer so as to coverthe light shielding layer, the laminates each comprising awettability-variable component layer and a colored layer provided in apredetermined pattern on the wettability-variable component layer in itsareas having specific wettability, the light shielding layer beinglocated at each boundary region between two adjacent colored layers.

In the color filter of the present invention, the areas having specificwettability may be areas having high critical surface tension.

In the color filter of the present invention, the wettability-variablecomponent layer may be a photocatalyst-containing layer comprising atleast a binder and a photocatalyst, the binder may contain anorganopolysiloxane prepared from a composition containing a chloro- oralkoxysilane, or the binder may contain an organopolysiloxane preparedfrom a composition containing a reactive silicone.

In the color filter of the present invention, the wettability-variablecomponent layer may be an organic polymer resin layer.

The present invention further provides a process for producing a colorfilter, comprising:

the first step of forming areas having specific wettability in apredetermined pattern on a transparent substrate and depositing acoating composition for a light shielding layer onto the areas havingspecific wettability to form a light shielding layer; and

the second step of forming areas having specific wettability in apredetermined pattern on the transparent substrate and depositing acoating composition for a colored layer onto the areas having specificwettability to form a colored layer.

In the first step, a photocatalyst-containing layer comprising at leasta binder and a photocatalyst may be formed on the transparent substrateand is then irradiated with light to permit light exposed areas to havehigh critical surface tension through photocatalytic action, therebyforming the areas having specific wettability, and, in the second step,the photocatalyst-containing layer is irradiated with light to permitlight exposed areas to have high critical surface tension throughphotocatalytic action, thereby forming the areas having specificwettability.

The present invention further provides a process for producing a colorfilter, comprising:

the first step of forming areas having specific wettability in apredetermined pattern on a transparent substrate provided with a lightshielding layer of a predetermined pattern; and

the second step of depositing a coating composition for a colored layeronto the areas having specific wettability to form a colored layer.

In the first step, a photocatalyst-containing layer comprising at leasta binder and a photocatalyst may be formed on the transparent substrateprovided with the light shielding layer of a predetermined pattern so asto cover the light shielding layer, followed by irradiation with lightto permit light exposed areas to have high critical surface tensionthrough photocatalytic action, thereby forming the areas having specificwettability.

The present invention further provides a process for producing a colorfilter, comprising repeating the procedure for forming areas havingspecific wettability in a predetermined pattern on a transparentsubstrate, provided with a light shielding layer of a predeterminedpattern, and depositing a coating composition for a colored layer ontothe areas having specific wettability to form a colored layer as manytimes as required to form a necessary number of colored layers of aplurality of colors.

In the above process for producing a color filter, aphotocatalyst-containing layer comprising at least a binder and aphotocatalyst may be formed on the transparent substrate provided withthe light shielding layer of a predetermined pattern so as to cover thelight shielding layer, followed by irradiation with light to permitlight exposed areas to have high critical surface tension throughphotocatalytic action, thereby forming the areas having specificwettability.

The present invention further provides a process for producing a colorfilter, comprising:

the first step of forming areas having specific wettability in apredetermined pattern on a transparent substrate and depositing acoating composition for a light shielding layer onto the areas havingspecific wettability to form a light shielding layer;

the second step of repeating the procedure for forming areas havingspecific wettability in a predetermined pattern on the transparentsubstrate and depositing a coating composition for a colored layer ontothe wettable areas to form a colored layer as many times as required toform a necessary number of colored layers of a plurality of colors.

In the first step, a photocatalyst-containing layer comprising at leasta binder and a photocatalyst may be formed on the transparent substratefollowed by irradiation with light to permit light exposed areas to havehigh critical surface tension through photocatalytic action, therebyforming the areas having specific wettability, and, in the second step,a photocatalyst-containing layer comprising at least a binder and aphotocatalyst may be formed so as to cover the light shielding layerfollowed by irradiation with light to permit light exposed areas to havehigh critical surface tension through photocatalytic action, therebyforming the areas having specific wettability.

In the above process for producing a color filter, exposure of thephotocatalyst-containing layer to light may be carried out by any one ofpattern-wise exposure through a mask and a light beam exposure.

In the above process for producing a color filter, the deposition of thecoating composition for a light shielding layer and/or the coatingcomposition for a colored layer may be carried out by any one of acoating method, a nozzle ejection method, and a vacuum thin filmformation method. In the vacuum thin film formation method, after theformation of a thin film, the thin film formed of a coating compositionfor a light shielding layer or a coating composition for a colored layerdeposited on areas other than the areas having specific wettability maybe removed.

In the above inventions, areas having specific wettability have highwettability by the composition for a light shielding layer and thecomposition for a colored layer, so that the composition for a lightshielding layer and the composition for a colored layer are selectivelydeposited only onto areas having specific wettability to form a lightshielding layer and a colored layer with high accuracy. Thephotocatalyst-containing layer in its light exposed areas are brought toa high critical surface tension state through photocatalytic action toform the above areas having specific wettability.

Re: Third Invention

The present inventors have found that selective deposition of a liquidcontaining a material for a lens onto a pattern based on a difference inwettability followed by curing to form a lens can attain the aboveobject. Specifically, the present invention provides a process forproducing a lens, comprising the steps of:

forming a pattern based on a difference in wettability on the surface ofa substrate;

depositing a liquid containing a material for a lens on the surface ofthe substrate in its areas having specific wettability; and

curing the liquid containing the material for a lens to form a lens.

Re: Fourth Invention D

The present invention provides a plate for lithography, comprising: asubstrate; a layer provided on the substrate, the wettability of thelayer being variable upon pattern-wise exposure; a resin layer providedon areas of which the wettability has been varied upon pattern-wiseexposure; and areas that have been hydrophilified or lipophilified uponwhole exposure.

In the plate for lithography, the layer of which the wettability isvariable upon exposure may comprise: a photocatalyst; and a material ofwhich the wettability is variable through photocatalytic action.

In the plate for lithography, the material of which the wettability isvariable may comprise a silicone resin.

In the plate for lithography, the resin layer may be ink repellent.

In the plate for lithography, the ink-repellent resin may be a siliconeresin.

In the plate for lithography, the ink-repellent resin layer may be asilicone resin layer that has been crosslinked by a condensationreaction of SiOH groups with a hydrolyzable crosslinking agent.

In the plate for lithography, the ink-repellent resin layer may be asilicone resin layer that has been crosslinked by an addition reactionof SiH groups with vinyl groups.

In the above plate for lithography, the resin layer may be ink receptiveand water repellent.

The present invention further provides a process for producing a platefor lithography, comprising the steps of: putting a layer onto asubstrate, the wettability of the layer being variable throughphotocatalytic action upon pattern-wise exposure; pattern-wise exposingthe layer; coating a resin composition to selectively form a resin layeron wettability-varied areas; and then conducting exposure to vary thewettability of areas not provided with the resin layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing one embodiment of the present invention;

FIG. 2 is a diagram showing another embodiment of the present invention;

FIG. 3 is a diagram showing still another embodiment of the presentinvention;

FIG. 4 is a diagram showing a further embodiment of the presentinvention;

FIG. 5 is a diagram showing the relationship between light irradiationtime and wettability of structures for pattern formation according tothe present invention;

FIG. 6 is a diagram showing a further embodiment of the presentinvention;

FIG. 7 is a diagram showing a further embodiment of the presentinvention;

FIG. 8 is a diagram showing the relationship between light irradiationtime and wettability of structures for pattern formation according tothe present invention;

FIG. 9 is a diagram showing one embodiment of the process for producingan element according to the present invention;

FIG. 10 is a diagram showing another embodiment of the process forproducing an element according to the present invention;

FIG. 11 is a diagram showing still another embodiment of the process forproducing an element according to the present invention;

FIG. 12 is a diagram showing a further embodiment of the process forproducing an element according to the present invention;

FIG. 13 is a schematic cross-sectional view showing one embodiment ofthe color filter according to the present invention;

FIG. 14 is a schematic cross-sectional view showing another embodimentof the color filter according to the present invention;

FIG. 15 is a schematic cross-sectional view showing still anotherembodiment of the color filter according to the present invention;

FIG. 16 is a schematic cross-sectional view showing a filter embodimentof the color filter according to the present invention;

FIG. 17 is a flow diagram illustrating one embodiment of the process forproducing a color filter according to the present invention;

FIG. 18 is a flow diagram illustrating another embodiment of the processfor producing a color filter according to the present invention;

FIG. 19 is a plan view showing the state of a mask at the time of lightexposure of a photocatalyst-containing layer in the process forproducing a color filter according to the present invention shown inFIG. 18;

FIG. 20 is a flow diagram illustrating another embodiment of the processfor producing a color filter according to the present invention;

FIG. 21 is a flow diagram illustrating still another embodiment of theprocess for producing a color filter according to the present invention;

FIG. 22 is a diagram illustrating regulation of the focal length in theprocess for producing a lens according to the present invention;

FIG. 23 is a cross-sectional view showing a microlens array according toa preferred embodiment of the present invention;

FIG. 24 is a cross-sectional view showing a color microlens arrayaccording to a preferred embodiment of the present invention;

FIG. 25 is a diagram illustrating the production process of a microlensusing a photocatalyst according to a preferred embodiment of the presentinvention;

FIG. 26 is a cross-sectional view showing one embodiment of a microlensarray having a light shielding layer according to a preferred embodimentof the present invention;

FIG. 27 is a plan view, showing a microlens array having a lightshielding layer according to a preferred embodiment of the presentinvention, as viewed from the light shielding layer side;

FIG. 28 is a cross-sectional view showing one embodiment of an imagepick-up device using a microlens array having a light shielding layeraccording to a preferred embodiment of the present invention;

FIG. 29 is a cross-sectional view showing one embodiment of an imagepick-up device comprising a color microlens array having a lightshielding layer according to a preferred embodiment of the presentinvention;

FIG. 30 is a cross-sectional view showing one embodiment of a displayusing a microlens array having a light shielding layer according to apreferred embodiment of the present invention;

FIG. 31 is a cross-sectional view showing one embodiment of a liquidcrystal display using a color microlens array having a light shieldinglayer according to a preferred embodiment of the present invention;

FIG. 32 is a diagram illustrating a process for producing a press plateof the printing plate according to the present invention;

FIG. 33 is a diagram illustrating a process for producing a press plateof the printing plate according to the present invention; and

FIG. 34 is a diagram illustrating a printing process using thelithographic plate according to the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Re: First Invention A

The present invention relates to a structure for pattern formation and amethod for pattern formation wherein a pattern is formed by utilizingthe action of a photocatalyst that, upon light irradiation, creates achemical change of materials present around it. According to the presentinvention, the pattern, when used in printing of designs, images,letters and the like, refers to areas that, upon transfer of theprinting ink, receive or repel the ink. Further, the structure forpattern formation according to the present invention may be utilized inapplications other than printing. In this case, the pattern connotesareas, formed on a structure for pattern formation in response to achange in wettability, having properties different from those aroundthem, and areas, on another substrate, obtained by transfer of the aboveareas onto the another substrate.

The mechanism of action of the photocatalyst typified by titanium oxideaccording to the present invention has not been frilly elucidated yet.However, it is considered that carriers produced by light irradiationinfluence the chemical structure of the organic material through adirect reaction with a neighboring compound, or otherwise by activeoxygen species produced in the presence of oxygen and water.

Proposals utilizing the photocatalytic action include one wherein oilstains are decomposed by light irradiation to hydrophilify the oilstains, enabling the oil stains to be washed away by water, one whereina hydrophilic film is formed on the surface of glass or the like toimpart antifogging properties, and one wherein aphotocatalyst-containing layer is formed on the surface of tiles or thelike to form the so-called antimicrobial tiles or the like that canreduce the number of bacteria floating in air.

Enhancement in receptivity of pattern areas to printing inks, toners orthe like, or repellency of non-pattern areas to ink or the like byutilizing a material of which the wettability is variable throughphotocatalytic action, a layer which can be decomposed and removed byphotocatalytic action, a layer containing a material of which thewettability is variable through photocatalytic action, a layer having acomposition comprising a material decomposable through photocatalyticaction and a binder and the like has realized the structure for patternformation according to the present invention.

Photocatalysts usable in the structure for pattern formation and themethod for pattern formation according to the present invention includemetal oxides known as photosemiconductors, such as titanium oxide(TiO₂), zinc oxide (ZnO), tin oxide (SnO₂), strontium titanium oxide(SrTiO₃), tungsten oxide (WO₃), bismuth oxide (Bi₂O₃), and iron oxide(Fe₂O₃). Among them, titanium oxide is particularly preferred because ithas high band gap energy and is chemically stable, nontoxic, and easilyavailable.

Titanium oxide may be in anatase form or rutile form with anatase formof titanium oxide being preferred.

Preferably, the anatase form of titanium has a small particle diameterbecause the photocatalytic reaction takes place efficiently. The averageparticle diameter is preferably not more than 50 nm, more preferably notmore than 20 nm. Examples of anatase form of titanium oxide usableherein include hydrochloric acid peptization type titania sols (STS-02,average crystal diameter 7 nm, manufactured by Ishihara Sangyo KaishaLtd.) and nitric acid peptization type titania sols (TA-15, averagecrystal diameter 12 nm, manufactured by Nissan Chemical IndustriesLtd.).

The photocatalyst-containing layer according to the present inventionmay be formed by dispersing a photocatalyst in a binder. Thephotocatalyst has a fear of decomposing the binder as well uponphotoexcitation. Therefore, the binder should have satisfactoryresistance to photo-oxidation by the photocatalyst. Further, when use ofthe structure for pattern formation as printing plates is taken intoconsideration, plate wear and abrasion resistance are also required ofthe photocatalyst-containing layer.

A silicone resin having siloxane bonds (—Si—O—) in its main skeleton maybe used as the binder that can satisfy the above requirements.

In the silicone resin, organic groups are bonded to silicon atoms. Asdescribed in detail in working examples, upon photoexcitation of thephotocatalyst, the organic groups bonded to silicon atoms in thesilicone molecule are replaced with oxygen-containing groups, resultingin improved wettability. Therefore, the silicone resin functions also asa material of which the wettability is variable.

The silicone resin may be a hydrolysis condensate or a cohydrolysiscondensate of at least one member selected from silicon compoundsrepresented by general formula Y_(n)SiX₄₋₄ wherein n is 1 to 3; Yrepresents an alkyl, fluoroalkyl, vinyl, amino, or epoxy group; and Xrepresents a halogen or a methoxyl, ethoxyl, or acetyl group.

Specific examples thereof include methyltrichlorosilane,methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane,methyltriisopropoxysilane, methyl-tri-t-butoxysilane;ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane,ethyltriethoxysilane, ethyltriisopropoxysilane,ethyl-tri-t-butoxysilane; n-propyltrichlorosilane,n-propyltribromosilane, n-propyltrimethoxysilane,n-propyltriethoxysilane, n-propyltriisopropoxysilane,n-propyl-tri-t-butoxysilane; n-hexytrichlorosilane,n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane,n-hexyltriisopropoxysilane, n-hexyl-tri-t-butoxysilane;n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane,n-decyltriethoxysilane, n-decyltriisopropoxysilane,n-decyl-tri-t-butoxysilane; n-octadecyltrichlorosilane,n-octadecyltribromosilane, n-octadecyltrimethoxysilane,n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane,n-octadecyl-tri-t-butoxysilane; phenyltrichlorosilane,phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane,phenyltrisopropoxysilane, phenyl-tri-t-butoxysilane; tetrachlorosilane,tetrabromosilane, tetramethoxysilane, tetraethoxysilane,tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldichlorosilane,dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane;diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane,diphenyldiethoxysilane; phenylmethyldichlorosilane,phenylmethyldibromosilane, phenylmethyldimethoxysilane,phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane,trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxyhydrosilane,ti-t-butoxyhydrosilane; vinyltrichlorosilane, vinyltibromosilane,vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane,vinyl-tri-t-butoxysilane; trifluoropropyltrichlorosilane,trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane,trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane,trifluoropropyl-tri-t-butoxysilane;γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropyltriisopropoxysilane,γ-glycidoxypropyl-tri-t-butoxysilane;γ-methacryloxypropylmethyldimethoxysilane,γ-methacryloxypropylmethyldiethoxysilane,γ-methacryloxypropyltrimethoxysilane,γ-methacryloxypropyltriethoxysilane,γ-methacryloxypropyltriisopropoxysilane,γ-methacryloxypropyl-tri-t-butoxysilane;γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropyltriisopropoxysilane, γ-aminopropyl-tri-t-butoxysilane;γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltnisopropoxysilane,γ-mercaptopropyl-tri-t-butoxysilane;β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltriethoxysilane; and partial hydrolyzatesthereof; and mixtures thereof.

When the binder layer comprises an organoalkoxysilane, preferably, 10 to30% by weight of the organoalkoxysilane is accounted for by abifunctional silicone precursor, for example, a dialkoxydimethylsilane.When use of the organoalkoxysilane in the sol-gel process iscontemplated, preferably, the organoalkoxysilane is composed mainly of atrialkoxymethylsilane which is a trifunctional silicone precursor fromthe viewpoint of improving the crosslinking density. When a differencein wettability is created as in the present invention, incorporation ofa large amount of dimethylsiloxane component rather than amethylsiloxane component can improve water repellency and oilrepellency.

The silicone molecule may contain fluoroalkyl groups as organic groupsbonded to silicon atoms. In this case, the critical surface tension ofunexposed areas are further lowered. Therefore, the repellency of theink and the composition for a functional layer by the unexposed areas isimproved, the function of inhibiting the deposition of the ink or thecomposition for a functional layer is increased, and, in addition, therange of usable materials for the ink or the composition for afunctional layer is increased.

Specifically, the silicone is formed from at least one member selectedfrom hydrolysis condensates and cohydrolysis condensates of thefollowing fluoroalkylsilanes. Compounds containing fluoroalkyl groupsinclude the following compounds. Compounds generally known asfluorosilane coupling agents may also be used.

-   -   CF₃(CF₂)₃CH₂CH₂Si(OCH₃)₃,    -   CF₃(CF₂)₅CH₂CH₂Si(OCH₃)₃,    -   CF₃(CF₂)₇CH₂CH₂Si(OCH₃)₃,    -   CF₃(CF₂)₉CH₂CH₂Si(OCH₃)₃,    -   (CF₃)₂CF(CF₂)₄CH₂ CH₂Si(OCH₃)₃,    -   (CF₃)₂CF(CF₂)₆CH₂CH₂Si(OCH₃)₃,    -   (CF₃)₂CF(CF₂)₈CH₂CH₂Si(OCH₃)₃,    -   CF₃(C₆H₄)C₂H₄Si(OCH₃)₃,    -   CF₃(CF₂)₃(C₆H₄)C₂H₄Si(OCH₃)₃,    -   CF₃(CF₂)₅(C₆H₄)C₂H₄Si(OCH₃)₃,    -   CF₃(CF₂)₇(C₆H₄)C₂H₄Si(OCH₃)₃,    -   CF₃(CF₂)₃CH₂CH₂SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₅CH₂CH₂SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₇CH₂CH₂SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)_(g)CH₂CH₂SiCH₃ (OCH₃)₂,    -   (CF₃)₂CF(CF₂)₄CH₂ CH₂SiCH₃ (OCH₃)₂,    -   (CF₃)₂CF(CF₂)₆CH₂ CH₂SiCH₃ (OCH₃)₂,    -   (CF₃)₂CF(CF₂)₈CH₂ CH₂SiCH₃ (OCH₃)₂,    -   CF₃(C₆H₄)C₂H₄SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₃(C₆H₄)C₂H₄SiCH₃(OCH₃)₂,    -   CF₃(CF₂)₅(C₆H₄)C₂H₄SiCH₃(OCH₃)₂,    -   CF₃(CF₂)₇(C₆H₄)C₂H₄SiCH₃(OCH₃)₂,    -   CF₃(CF₂)₃ CH₂ CH₂Si(OCH₂ CH₃)₃,    -   CF₃(CF₂)₅ CH₂ CH₂Si(OCH₂ CH₃)₃,    -   CF₃(CF₂)₇ CH₂ CH₂Si(OCH₂ CH₃)₃,    -   CF₃(CF₂)₉ CH₂ CH₂Si(OCH₂ CH₃)₃, and    -   CF₃(CF₂)₇SO₂N(C₂H₅)CH₂CH₂CH₂Si(OCH₃)₃

In order to provide better repellency of the ink and the composition fora functional layer by unexposed areas, the silicone is preferably areactive linear silicone, more preferred a silicone prepared bycrosslinking dimethylpolysiloxane at low crosslinking density.Typically, silicones obtained by crosslinking compounds comprising thefollowing repeating units are preferred:

wherein n is an integer of two or more; and R¹ and R² represent asubstituted or unsubstituted alkyl, alkenyl, aryl, or cyanoalkyl grouphaving 1 to 10 carbon atoms. R¹ and R² preferably represent a methylgroup because the surface free energy of the silicone is the smallest.The molar proportion of the methyl group is preferably not less than600%.

The molecular weight of the silicone is preferably 500 to 1,000,000.When the molecular weight is excessively small, the content of R¹ and R²is relatively low, making it difficult to develop the water repellency,oil repellency and the like. On the other hand, when the molecularweight is excessively large, the content of the end in X and Y is low,posing a problem that the crossing density is small.

X and Y, which may be the same or different, are selected from thefollowing groups. R represents a hydrocarbon chain having 10 or lesscarbon atoms.

Reactive modified silicones usable in the present invention may beeither one wherein crosslinking is performed by condensation or onewherein crosslinking is performed in the presence of a crosslinkingagent. When the crosslinking is performed by condensation, a tin, zinc,lead, calcium, or manganese salt of carboxylic acid, preferably, alaurate or chloroplatinic acid, may be added as a catalyst.

On the other hand, when the crosslinking is performed in the presence ofa crosslinking agent, crosslinking agents usable herein includeisocyanates commonly used as crosslinking agents in the art. Preferredexamples thereof are as follows:

The reactive silicone compound may be of aqueous emulsion type. Theaqueous emulsion type compound is easy to handle because an aqueoussolvent is used.

According to the present invention, the water repellency and the oilrepellency may be enhanced by incorporating the reactive siliconecompound as the binder in combination with a stable organosiloxanecompound that does not cause any crosslinking reaction, such asdimethylpolysiloxane.

In this case, not less than 60% by weight of the siloxane contained in alayer formed from a compound containing a reactive silicone compound ispreferably accounted for by the siloxane obtained from the reactivesilicone compound. When the proportion is less than 60% by weight, theamount of dimethylsiloxane is reduced, unfavorably resulting indeteriorated water repellency and oil repellency.

The binder may be an amorphous silica precursor. Preferred are siliconcompounds represented by general formula SiX₄ wherein X represents ahalogen, a methoxy, ethoxy, or acetyl group or the like, silanols whichare hydrolyzates of the silicon compounds, and polysiloxanes having anaverage molecular weight of not more than 3000.

Specific examples thereof include tetraethoxysilane,tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, andtetramethoxysilane. In this case, a photocatalyst-containing film may beformed by homogeneously dispersing an amorphous silica precursor andphotocatalyst particles in a nonaqueous solvent, utilizing moisture inair to form a silanol through hydrolysis on a substrate, and conductingdehydropolycondensation at room temperature. When thedehydropolycondensation of the silanol is carried out at 100° C. orabove, the degree of polymerization is increased, realizing improvedstrength of the film surface. These binders may be used alone or as amixture of two or more.

Titanium oxide alone may be used for the film formation without use ofany binder. In this case, amorphous titania is formed on a substratefollowed by firing to cause a phase change to crystalline titania. Theamorphous titania may be obtained, for example, by hydrolyzing anddehydrocondensing an inorganic salt of titanium, such as titaniumtetrachloride, titanium sulfate, or hydrolyzing and dehydrocondensing anorganotitanium compound, such as tetraethoxytitanium,tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium,or tetramethoxytitanium, in the presence of an acid.

Next, the amorphous titania may be transformed to anatase form oftitania by firing at 400 to 500-C and may be transformed to rutile formof titania by filing at 600 to 700° C.

In the layer containing at least one of an organosiloxane and amorphoussilica, and a photocatalyst, the content of photocatalyst is preferably5 to 60% by weight, more preferably 20 to 400% by weight.

The photocatalyst and the binder may be dispersed in a solvent toprepare a coating liquid followed by coating of the liquid. Solventsusable herein include alcoholic organic solvents, such as ethanol andisopropanol.

Titanium, aluminum, zirconium, and chromium coupling agents may also beused.

The photocatalyst-containing coating liquid may be coated onto thesubstrate by spray coating, dip coating, roll coating, bead coating orthe like. When an ultraviolet curable component is contained as thebinder, curing by ultraviolet irradiation results in the formation of aphotocatalyst-containing composition layer on the substrate.

The excitation wavelength of the anatase form of titania is not morethan 380 nm. Therefore, the excitation of this type of photocatalystsshould be carried out using ultraviolet light. Ultraviolet light sourcesusable herein include mercury lamps, metal halide lamps, xenon lamps,excimer lamps, excimer layer, YAG laser, and other ultraviolet lightsources. The wettability of the film surface may be varied by varyingthe ultraviolet light intensity, exposure and the like.

When the exposure is carried out using a fine beam of a laser or thelike, a desired image pattern may be directly formed without use of anymask. In the case of other light sources, a pattern is formed by lightirradiation using a mask with a desired pattern formed thereon. Patternforming masks usable herein include masks wherein a pattern is formed ona metal sheet, such as vapor deposition masks, photomasks wherein apattern is formed using a metallic chromium on a glass sheet, and, forprinting applications, plate preparation films.

The structure for pattern formation may be rendered sensitive to visibleand other wavelengths by doping with metal ions of chromium, platinum,palladium or the like, by addition of fluorescent materials, or additionof photosensitive dyes. Examples of dyes usable herein include cyaninedyes, carbocyanine dyes, dicarbocyanine dyes, hemicyanine dyes, andother cyanine dyes. Other useful dyes include diphenylmethane dyes, forexample, triphenylmethane dyes, such as Crystal Violet and basicfuchsine, xanthene dyes, such as Rhodamine B, Victoria Blue, BrilliantGreen, Malachite Green, Methylene Blue, pyrylium salts, benzopyryliumsalts, trimethylbenzopyrylium salts, and triallylcarbonium salts.

When a mask is used in exposing the structure for pattern formationaccording to the present invention, the resolution can be enhanced byconducting the exposure in intimate contact of the mask with thephotocatalyst-containing layer. In this case, however, the sensitivityis remarkably lowered. Preferably, the exposure is carried out whileleaving a spacing of about 100 μm between the mask and thephotocatalyst-containing layer.

Exposure while blowing air into between the mask and the structure forpattern formation can accelerate the reaction and can improve thesensitivity and, in addition, can prevent heterogeneous exposure derivedfrom a difference in position between the center portion and the portionaround the portion. Further, exposure while heating of the structure forpattern formation can improve the sensitivity. Furthermore, a finepattern may also be formed by reduction projection exposure wherein theimage of a mask pattern is reduced using a reduction optical system.

Substrates usable in the structure for pattern formation according tothe present invention include glasses, metals, such as aluminum andalloys thereof, plastics, woven fabrics, and nonwoven fabrics that areused according to application of the structure for pattern formation orelements with a pattern formed thereon. According to the structure forpattern formation according to the present invention, prior to thecoating of the composition for a photocatalyst-contain g layer, a primerlayer may be formed on the substrate from the viewpoints of animprovement in adhesion, an improvement in surface roughness, theprevention of substrates from being deteriorated through photocatalyticaction, the prevention of a lowering in photocatalytic activity and thelike. Materials for the primer layer usable herein include resinscomposed mainly of a siloxane structure, fluororesins, epoxy resins, andpolyurethane resins.

According to one embodiment of the structure for pattern formationaccording to the present invention, as shown in FIG. 1 (A), a structure101 for pattern formation may comprise a photocatalyst-containing layer141 provided either directly or through a primer layer 103 on asubstrate 102. As shown in FIG. 1 (B), in order to record patterninformation, exposure 106 is carried out in a predetermined pattern 105.As shown in FIG. 1 (C), allyl chains of the silicone compound areconverted to OH groups through the action of a photocatalyst 107, andhigh critical surface tension areas 108 are formed in the surface havinglow critical surface tension according to the exposed pattern,permitting pattern information to be recorded by utilizing a differencein wettability between the high critical surface tension areas 108 andthe low critical surface tension areas 109.

The structure for pattern formation according to a second embodiment ofthe present invention, as shown in FIG. 2 (A), comprises a substrate102, a primer layer 103 provided on the substrate 102, aphotocatalyst-containing layer 142 provided on the primer layer 103, anda wettability-variable material layer 110 provided on thephotocatalyst-containing layer 142, the wettability of thewettability-variable material layer 110 being variable throughphotocatalytic action upon exposure to light. As shown in FIG. 2 (B),exposure 106 is carried out in a pattern 105 to form, as shown in FIG. 2(C), areas 111 having specific wettability according to the pattern.Thus, pattern information is recorded.

In the case of the second embodiment, a photocatalyst-containing layerof a hydrolyzate or a partial hydrolyzate of a composition comprising aphotocatalyst dispersed in a binder precursor or the like is formed, anda thin film an organic material having low critical surface tensionsthen formed. The photocatalyst layer may be formed by the photocatalystper se. The thin film of an organic material may be used by solutioncoating, surface grafting, surfactant treatment, or gaseous phase filmformation such as PVD or CVD.

Organic materials usable herein include monomeric compounds, polymericcompounds, and surfactants, the wettability of these materials beingvariable by the photocatalyst.

Specific examples of organic materials usable herein include silanecompounds that permit organic groups to be converted to hydroxyl groupsthrough photocatalytic action, such as silane coupling agents,chlorosilanes, alkoxysilanes, or hydrolysis condensates and cohydrolysiscondensates of two or more of them.

The structure for pattern formation according to a third embodiment ofthe present invention, as shown in FIG. 3 (A), comprises a substrate102, a photocatalyst-containing layer 143 provided on the substrate 102,and a material layer 112 provided on the photocatalyst-containing layer143, the layer 112 being formed of a material that, upon lightirradiation, can be decomposed and removed through photocatalyticaction. As shown in FIG. 3 (B), exposure 106 is carried out in a pattern105, and, as shown in FIG. 3 (C), areas having specific wettability 113are formed according to the pattern. Thus, pattern information isrecorded.

In the third embodiment, a photocatalyst-containing layer of ahydrolyzate or a partial hydrolyzate of a composition comprising aphotocatalyst dispersed in a binder precursor or the like is formed, anda thin film of an organic material having low critical surface tensionis then formed. The catalyst layer may be formed by the photocatalystper se. The thin film of an organic material may be used by solutioncoating, surface grafting, surfactant treatment, or gaseous phase filmformation such as PVD or CVD.

Specific examples of organic materials usable herein include hydrocarbonnonionic surfactants, such as NIKKOL BL, BC, BO, and BB seriesmanufactured by Nihon Surfactant Kogyo K.K.; and fluoro or siliconenonionic surfactants, such as ZONYL FSN and FSO, manufactured by E.I. duPont de Nemours & Co., SurfluonS-141 and 145 manufactured by Asahi GlassCo., Ltd., Megafac F-141 and 144 manufactured by Dainippon Ink andChemicals, Inc., Ftergent F-200 and F-251, manufactured by Neos Co.,Ltd.; Unidyne DS-401 and 402 manufactured by Daikin Industries, Ltd.,and Fluorad FC-170 and 176 manufactured by Sumitomo 3M Ltd. Cationic,anionic, and amphoteric surfactants may also be used.

Examples of organic materials other than surfactants usable hereininclude oligomers and polymers, such as polyvinyl alcohol, unsaturatedpolyesters, acrylic resins, polyethylene, diallyl phthalate, ethylenepropylene diene monomer, epoxy resin, phenolic resin, polyurethane,melamine resin, polycarbonate, polyvinyl chloride, polyamide, polyimide,styrene butadiene rubber, chloroprene rubber, polypropylene,polybutylene, polystyrene, polyvinyl acetate, nylon, polyester,polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin,polysulfide, and polyisoprene.

The structure for pattern formation according to a fourth embodiment ofthe present invention, as shown in FIG. 4 (A), comprises a substrate102, a primer layer 103 provided on the substrate 102, and aphotocatalyst-containing layer 144 containing a photocatalyst, a binder,and a photocatalytically decomposable material 116, comprising ahydrophobic portion 114 and a hydrophilic portion 115, decomposablethrough photocatalytic action upon exposure to light. A layer consistingof the photocatalyst and the photocatalytically decomposable materialalone may be formed instead of the photocatalyst-containing layer. Asshown in FIG. 4 (B), exposure 106 is carried out in a predeterminedpattern 105. As a result, as shown in FIG. 4 (C), the photocatalyticallydecomposable material 116 comprising the hydrophobic portion 114 and thehydrophilic portion 115 present in predetermined areas is decomposed byphotocatalytic action to form areas 117 of which the surface wettabilityhas been varied according to the exposed 106 pattern. Thus, patterninformation is recorded.

Preferred materials capable of varying the wettability of the surfaceinclude those that can regulate the wettability of thephotocatalyst-containing layer as desired by varying the kind and amountthereof added, for example, surfactants.

Surfactants are preferred as the material capable of varying thewettability, and specific examples thereof include hydrocarbon nonionicsurfactants, such as NIKKOL BL, BC, BO, and BB series manufactured byNihon Surfactant Kogyo K.K.; and fluoro or silicone nonionicsurfactants, such as ZONYL FSN and FSO, manufactured by E.I. du Pont deNemours & Co., SurfluonS-141 and 145 manufactured by Asahi Glass Co.,Ltd., Megafac F-141 and 144 manufactured by Dainippon Ink and Chemicals,Inc., Ftergent F-200 and F-251, manufactured by Neos Co., Ltd.; UnidyneDS-401 and 402 manufactured by Daikin Industries, Ltd., and FluoradFC-170 and 176 manufactured by Sumitomo 3M Ltd. Cationic, anionic, andamphoteric surfactants may also be used.

Examples of organic materials other than surfactants usable hereininclude oligomers and polymers, such as polyvinyl alcohol, unsaturatedpolyesters, acrylic resins, polyethylene, diallyl phthalate, ethylenepropylene diene monomer, epoxy resin, phenolic resin, polyurethane,melamine resin, polycarbonate, polyvinyl chloride, polyamide, polyimide,styrene butadiene rubber, chloroprene rubber, polypropylene,polybutylene, polystyrene, polyvinyl acetate, nylon, polyester,polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin,polysulfide, and polyisoprene.

Use of a composition comprising 5 to 60% by weight of the photocatalyst,95 to 400% by weight of amorphous silica, and 0.1 to 55% by weight ofthe material of which the wettability is variable through photocatalyticaction is preferred.

According to the structure for pattern formation of the presentinvention, the surface free energy is varied through the action of thecatalyst in the composition, and the wettability-varied areas havevaried receptivity to printing ink. Therefore, the structure for patternformation may be used as printing plates. Use of the structure forpattern formation according to the present invention as an originalplate for a printing plate can eliminate the need to provide the step ofwet development and the like and can offer a feature that thepreparation of a printing plate is completed simultaneously withexposure. The formation of a pattern on the structure for patternformation according to the present invention may be performed byexposure through a process film or the like or by direct patternformation using a laser or the like.

In preparing an original plate for a printing plate, substrates usableherein include those commonly used in offset printing plates, such asaluminum. Alternatively, a pattern may be formed by coating aphotocatalyst-contain g layer onto a screen of a woven fabric or anonwoven fabric and exposing the photocatalyst-containing layer. Whenthe substrate is constituted by a material, such as a plastic, that hasa fear of being deteriorated by the photo-oxidation activity of thephotocatalyst, a silicone, a fluororesin or the like may be previouslycoated onto the substrate to form a protective layer. The substrate maybe in any desired form, such as a sheet, a ribbon, or a roll.

A photochromic material, which undergoes a change in color upon exposureto light, such as spiropyrone, or an organic dye decomposable throughphotocatalytic action may be incorporated into the composition to form avisualized pattern.

When unexposed areas are designed to be receptive to printing ink andrepellent to dampening water, the structure for pattern formationaccording to the present invention may be used also as conventionaloffset printing plates using dampening water.

When use of the structure for pattern formation according to the presentinvention as an element with a pattern laminated thereon iscontemplated, various functional layers may be formed in a pattern formon various substrates by regulating the wettability of the surface ofthe structure for pattern formation. Functional properties refer tooptical properties (such as refraction, light selective absorption,reflection, polarization, light transmission, light selectivetransmission, nonlinear optical properties, luminescence of phosphor orphosphorescence, and photochromism), magnetic properties (such as hardmagnetic properties, soft magnetic properties, nonmagnetic properties,and magnetic permeability), electric and electronic properties (such aselectric conductivity, insulating properties, piezoelectric properties,pyroelectric properties, and dielectric properties), chemical properties(such as adsorption, desorption, catalytic activity, water absorption,oil absorption, ion conductivity, oxidation reduction properties,electrochemical properties, and electrochromic properties), mechanicalproperties (such as abrasion resistance), thermal properties (such asheat transfer, heat insulation, and infrared radiation properties), andbiological functions (such as biocompatibility and antithrombogenicity).

Functional elements may be prepared by coating a composition for afunctional layer onto a structure for pattern formation. The compositionfor a functional layer may be a composition that enables only one ofunexposed areas and exposed areas in the structure for pattern formationwith a pattern formed thereon to be wetted.

For the pattern, the numerical value of the wettability is not limitedso far as the surface of the pattern has areas different from each otherin wettability, that is, functional layer composition-depositable areasand functional layer composition-undepositable areas. The surface havingareas different from each other in wettability may be the surface of thesubstrate per se or the substrate surface after surface treatment suchas dampening water treatment.

Although no particular limitation is imposed, for example, when thesurface having areas different from each other in wettability is thesurface of the substrate per se, preferably, the unexposed areas of thestructure for pattern formation have a critical surface tension of notmore than 50 mN/m, preferably not more than 30 mN/m. Preferred materialsinclude silicone resin and silicone resin having a fluorocarbon group.The composition for a functional layer preferably comprises a materialhaving a higher surface tension than the critical surface tension on theunexposed areas of the structure for pattern formation.

In this case, compositions for a functional layer usable herein includeliquid compositions of ultraviolet curable monomers or the like notdiluted with any solvent and liquid compositions diluted with solvents.In the case of liquid compositions diluted with solvents, preferredsolvents are those having high surface tension, such as water andethylene glycol.

The lower the viscosity of the composition for a functional layer, theshorter the pattern formation time. In the case of liquid compositionsdiluted with solvents, an increase in viscosity due to evaporation ofsolvents and a change in surface tension occur at the time of patternformation. Therefore, the solvents preferably have low volatility.

The composition for a functional layer may be applied by coating means,such as dip coating, roll coating, or blade coating, nozzle ejectionmeans including ink jetting, electroless plating or the like. When thecomposition for a functional layer contains as a binder a componentcurable by ultraviolet light, heat, electron beams or the like, curingtreatment permits a pattern of various functional layers to be formedthrough the structure for pattern formation on the substrate.

After the formation of a functional layer on the whole area, thefunctional layer in its portions on the unexposed areas may be removedby utilizing a difference in adhesion between the interface of exposedareas/functional layer and the interface of unexposed areas/functionallayer, for example, by post treatment, such as intimate contact with apressure-sensitive adhesive tape followed by separation of thefunctional layer in its contemplated areas, blowing of air, or solventtreatment, thereby performing patterning.

The unexposed areas and the exposed areas are not required to completelyrepel the functional layer or to permit the functional layer to becompletely deposited thereon, and a pattern of areas different from eachother in amount of deposition due to different adhesion may be formed.

Further, the functional layer may be formed by vacuum formation such asPID or CVD. Even when the functional layer is formed on the whole area,utilization of a difference between adhesion of exposed areas tofunctional layer and the adhesion of unexposed areas to functional layerenables patterning, for example, by post treatment, for example,separation using a pressure-sensitive adhesive tape, blowing of air, orsolvent treatment, thereby performing patterning. In the case of filmformation using vacuum, the functional layer may be laminated on thewhole area of the structure for pattern formation, or alternatively,reactivity with the exposed areas or the unexposed areas may be utilizedto selectively form the functional layer on the exposed areas or theunexposed areas.

Compositions for a functional layer include those wherein properties ofthe functional layer can be developed by mere formation of a functionallayer on the structure for pattern formation and those wherein mereformation of a functional layer on the structure for pattern formationdoes not develop properties of the functional layer and, after the layerformation, post treatment, such as chemical treatment, ultraviolettreatment, or heat treatment, is necessary.

Next, elements which can be prepared using the structure for patternformation according to the present invention will be described.

Color filters for liquid crystal display devices and the like have ahigh definition pattern with a plurality of color pixels of red, green,blue and the like formed thereon. Application of the structure forpattern formation according to the present invention can realize theproduction of high definition color filters. For example, pattern-wiseexposure of a photocatalyst-containing layer provided on a transparentglass substrate followed by coating of a colored layer composition for acolor filter onto the exposed photocatalyst-containing layer permits thecolored layer composition to be coated only onto exposed areas due to achange in wettability of the exposed areas. This can reduce the amountof the composition for a colored layer used. Further, since the layer ofthe composition for a colored layer is formed only onto the pattern, useof a photosensitive resin composition as the composition for a coloredlayer can eliminate the need to provide the step of development or thelike, and simple photocuring after the coating can provide a highresolution color filter.

The structure for pattern formation according to the present inventionmay be used in the production of microlenses. For example, light iscircularly applied to the photocatalyst-containing layer provided on thetransparent substrate to form a wettability-varied circular pattern.When a composition for a lens is then dropped on wettability-variedareas, the droplets are spread only onto the exposed areas, and furtherdropping of the composition results in varied contact angle of thedroplet. Subsequent curing provides lenses having various shapes orfocal lengths. Therefore, high definition microlenses can be obtained.

Use of the structure for pattern formation according to the presentinvention in metal film formation by electroless plating results in theformation of metal films of a desired pattern.

For example, a desired metal pattern may be formed by applying light tothe structure for pattern formation according to the present inventionto form a pattern of areas having predetermined increased criticalsurface tension, i.e., high critical surface tension areas, treating thehigh critical surface tension areas with a pretreatment liquid forchemical plating and immersing the pretreated material in a chemicalplating liquid to form a desired metal pattern. According to thismethod, a metal pattern can be formed without the formation of a resistpattern, making it possible to produce printed boards, electroniccircuit elements and the like.

The structure for pattern formation according to the present inventionmay be used in the formation of a metal or other pattern by filmformation techniques using vacuum.

For example, a pattern having higher adhesion is prepared by lightirradiation, and a metal component, such as aluminum, is then heated invacuo to deposit the meal component on the whole area of the structurefor pattern formation to form a thin meal film. Since there is adifference in bond strength of thin metal layer between pattern-formedareas and pattern-unformed areas, a patterned thin metal layer may beformed by pressing a pressure sensitive adhesive against the surface ofthe thin film and removing the thin film, or by removing the thin filmwith a chemical.

When the removal is carried out using a pressure sensitive adhesive,bringing the adhesive face of a sheet coated with a pressure sensitiveadhesive into contact with the surface of the thin film followed byseparation of the sheet coated with the pressure sensitive adhesivepermits the thin film in its areas other than the pattern-formed areasto be separated due to a difference in adhesion between thepattern-formed areas and the pattern-unformed areas. Thus, a metalpattern call be formed. According to this method, a metal pattern can beformed without the formation of any resist pattern. This makes itpossible to prepare printed boards, electronic circuit elements and thelike having a higher definition pattern than the printing method.

The process for producing an element according to the present inventionwill be described with reference to the accompanying drawings.

FIG. 9 is a cross-sectional view illustrating one embodiment of theprocess for producing an element according to the present Invention.

In the step of pattern-wise exposure shown in FIG. 9 (A), as shown inA1, a structure 101 for pattern formation comprising a substrate 102having thereon a photocatalyst-containing layer 104 is subjected toexposure 106 through a photomask 120 according to a pattern of anelement to be formed. Alternatively, as shown in A2, a pattern is formeddirectly on the structure 101 for pattern formation by a laser 121having a wavelength in an ultraviolet region or the like. Thus, areas113 having specific wettability are formed on the surface of thestructure for pattern formation.

Next, in the step of forming a film on the whole area shown in FIG. 9(B), a functional layer 125 is formed on the whole area of the structurefor pattern formation by coating using a blade coater 122 as shown inB1, by coating using a spin coater 123 as shown in B2, or by filmformation means 124 utilizing vacuum, such as CVD, as shown in B3.

The exposed areas and the unexposed areas of the functional layer 125provided on the structure for pattern formation are different from eachother in adhesion due to a difference in surface free energy created byexposure of the structure for pattern formation.

Next, in the step of separation shown in FIG. 9 (C), a functional layer128 is formed by bringing the adhesive face of a pressure sensitiveadhesive tape 126 into intimate contact with the functional layer andseparating the tape from the end of the functional layer to remove thefunctional layer in its areas formed on the unexposed areas, by ejectingair through an air ejection nozzle 127, or by removing the functionallayer in its areas having low adhesion with the aid of a release agent.

FIG. 10 is a cross-sectional view illustrating another embodiment of theprocess for producing an element according to the present invention.

As with the process shown in FIG. 9, in the process shown in FIG. 10, afunctional layer 125 is formed on a structure 101 for pattern formationby a method as shown in FIG. 10 (A). Subsequently, as shown in FIG. 10(B), a substrate 129 for element formation is brought into intimatecontact with the functional layer.

As shown in FIG. 10 (C), the functional layer 125 is transferred ontothe substrate 129 for element formation to prepare an element having afunctional layer 128.

FIG. 11 is a cross-sectional view illustrating still another embodimentof the process for producing an element according to the presentinvention.

As shown in FIG. 11 (A), a structure 101 for pattern formationcomprising a substrate 102 having thereon a photocatalyst-containinglayer 104 is subjected to exposure 106 according to a pattern of anelement to be formed through a photomask 120. Thus, areas 113 havingspecific wettability are formed.

Next, as shown in FIG. 11 (B), a thermal transfer material 132comprising a hot-melt composition layer 131 provided on a sheet 130 isput on the structure for pattern formation so that the surface of thehot-melt composition layer faces the exposed surface of the structurefor pattern formation.

As shown in FIG. 11 (C), a hot plate 133 is then pressed against thethermal transfer material 132 on its sheet side.

As shown in FIG. 11 (D), after cooling, the thermal transfer material132 is removed to finally form a pattern 105 as shown in FIG. 11 (E).

FIG. 12 is a cross-sectional view illustrating a further embodiment ofthe process for producing an element according to the present invention.

As shown in FIG. 12 (A), a structure 101 for pattern formation isexposed through a photomask 102 to form unexposed areas and areas 113having specific wettability.

As shown in FIG. 12 (B), an ultraviolet curable resin composition 136 isejected through an ejection nozzle 135 toward the wettability-variedareas 113.

As shown in FIG. 12 (C), the ultraviolet curable resin compositionejected onto the exposed areas is risen due to a difference in surfacetension created by a difference in wettability between the unexposedareas and the exposed areas.

Next, as shown in FIG. 12 (D), ultraviolet light 137 for curing can beapplied to form microlenses 138.

Re: Second Invention B

The best mode for carrying out the invention will be described withreference to the accompanying drawings.

Color Filter of Present Invention

FIG. 13 is a schematic longitudinal sectional view showing oneembodiment of the color filter according to the present invention. InFIG. 13, a color filter 201 according to the present invention comprisesa transparent substrate 202, a photocatalyst-containing layer 203 as awettability-variable component layer provided on the transparentsubstrate 202, a black matrix (a light shielding layer) 204 and acolored layer 205 of a plurality of colors provided on thephotocatalyst-containing layer 203 in its areas having specificwettability (high critical surface tension areas), and a protectivelayer 206 provided so as to cover the black matrix 204 and the coloredlayer 205. In this color filter 201, the black matrix 204 is located ateach boundary region between two adjacent colored layers 205.

FIG. 14 is a schematic longitudinal sectional view showing anotherembodiment of the color filter according to the present invention. InFIG. 14, a color filter 211 according to the present invention comprisesa transparent substrate 212, a black matrix (a light shielding layer)214 provided on the transparent substrate 212, aphotocatalyst-containing layer 213 as a wettability-variable componentlayer provided on the transparent substrate 212 so as to cover the blackmatrix 214, a colored layer 215 of a plurality of colors provided on thephotocatalyst-containing layer 213 in its areas having specificwettability (high critical surface tension areas), and a protectivelayer 216 provided so as to cover the colored layer 215. In this colorfilter 211, the black matrix 214 is located at each boundary regionbetween two adjacent colored layers 215.

FIG. 15 is a schematic longitudinal sectional view showing still anotherembodiment of the color filter according to the present invention. InFIG. 15, a color filter 221 according to the present inventioncomprises: a transparent substrate 222; a black matrix (a lightshielding layer) 224 provided on the transparent substrate 222; providedon the transparent substrate 222 so as to cover the black matrix 224 inthe following order, a laminate comprising a photocatalyst-containinglayer 223 a as a first wettability-variable component layer and a redcolored layer 225R provided on the photocatalyst-containing layer 223 ain its areas having specific wettability (high critical surface tensionareas), a laminate comprising a photocatalyst-containing layer 223 b asa second wettability variable component layer and a green colored layer225G provided on the photocatalyst-containing layer 223 b in its areashaving specific wettability (high critical surface tension areas), and alaminate comprising a photocatalyst-containing layer 223 c as a thirdwettability-variable component layer and a blue colored layer 225Bprovided on the photocatalyst-containing layer 223 c in its areas havingspecific wettability (high critical surface tension areas); and aprotective layer 226 provided so as to cover the colored layer 225. Inthis color filter 221, the black matrix 224 is located at each boundaryregion between two adjacent colored layers 225.

FIG. 16 is a schematic longitudinal sectional view showing a furtherembodiment of the color filter according to the present invention. InFIG. 16, a color filter 231 according to the present inventioncomprises: a transparent substrate 232; a photocatalyst-containing layer233 a as a first wettability-variable component layer provided on thetransparent substrate 232; a black matrix (a light shielding layer) 234provided on the photocatalyst-containing layer 233 a in its areas havingspecific wettability (high critical surface tension areas); provided onthe first photocatalyst-containing layer 233 a so as to cover the blackmatrix 234 in the following order, a laminate comprising aphotocatalyst-containing layer 233 b as a second wettability-variablecomponent layer and a red colored layer 235R provided on thephotocatalyst-containing layer 233 b in its areas having specificwettability high critical surface tension areas), a laminate comprisinga photocatalyst-containing layer 233 c as a third wettability-variablecomponent layer and a green colored layer 235G provided on thephotocatalyst-containing layer 233 c in its areas having specificwettability (high critical surface tension areas), and a laminatecomprising a photocatalyst-containing layer 233 d as a fourthwettability-variable component layer and a blue colored layer 235Bprovided on the photocatalyst-containing layer 233 d in its areas havingspecific wettability (high critical surface tension areas); and aprotective layer 236 provided so as to cover the colored layer 235. Inthis color filter 231, the black matrix 234 is located at each boundaryregion between two adjacent colored layers 235.

Next, the construction of color filters according to the presentinvention will be described.

(Transparent Substrate)

Materials for transparent substrates 202, 212, 222, and 232 constitutingthe color filters 201, 211, 221, and 231 include transparent rigidmaterials, such as quartz glass, Pyrex glass, and synthetic quartzsheets, and flexible transparent flexible materials, such as transparentresin films and optical resin sheets. Among them, particularly glass7059 manufactured by Corning has small coefficient of thermal expansionand hence has excellent dimensional stability and workability in heattreatment at a high temperature. Further, this glass is an alkali-freeglass not containing an alkali component and hence is suitable in colorfilters for active matrix type color liquid crystal display derives.

(Wettability-Variable Component Layer)

The photocatalyst-containing layer 203, 213, 223, or 233 as thewettability-variable component layer constituting the color filter 201,211, 221, or 231 comprises at least a binder and a photocatalyst and,upon exposure to light, permits the critical surface tension to beincreased through photocatalytic action to form a high critical surfacetension layer.

The mechanism of the following action of the photocatalyst typified bytitanium oxide, in the photocatalyst-containing layer according to thepresent invention has not been fully elucidated yet However, it isconsidered that carriers produced by light irradiation changes thechemical structure of the organic material through a direct reactionwith a neighboring compound, or otherwise active oxygen species producedin the presence of oxygen and water.

Proposals utilizing the photocatalytic action include one wherein oilstains are decomposed by light irradiation to hydrophilify the oilstains, enabling the oil stains to be washed away by water, one whereina high critical surface tension layer is formed on the surface of glassor the like to impart antifogging properties, and one wherein aphotocatalyst-containing layer is formed on the surface of tiles or thelike to form the so-called antimicrobial tiles or the like that canreduce the number of bacteria floating in air.

According to the present invention, when a photocatalyst-containinglayer is used as the wettability-variable component layer, thephotocatalyst varies the wettability of light exposed areas through theaction of organic groups as a part of the binder or the oxidation,decomposition or the like of additives to bring the exposed areas to ahigh critical surface tension state, creating a large difference inwettability between exposed areas and unexposed areas and enhancing thereceptivity and repellency to the composition for a light shieldinglayer and the composition for a colored layer. This can realize thecolor filter.

The surface having high critical surface tension is not limited by thenumerical value of the wettability. However, for example, thewettability in terms of contact angle with water is preferably not morethan 40°, more preferably not more than 10°. In the present invention,the contact angle may be measured by dropping a water droplet on thesurface through a microsyringe and, 30 sec after that, measuring thecontact angle using a contact angle goniometer (Model CA-Z, manufacturedby Kyowa Interface Science Co., Ltd.).

Photocatalysts usable in the present invention include metal oxidesknown as photosemiconductors, such as titanium oxide (TiO₂), zinc oxide(ZnO), tin oxide (SnO₂), strontium titanate (SrTiO₃), tungsten oxide(WO₃), bismuth oxide (Bi₂O₃), and iron oxide (Fe₂O₃). Among them,titanium oxide is particularly preferred because it has high band gapenergy and is chemically stable, nontoxic, and easily available.

Titanium oxide may be in anatase form or rutile form with anatase formof titanium oxide being preferred. The excitation wavelength of theanatase form of titanium oxide is not more than 380 nm. Examples of theanatase form of titanium oxide include hydrochloric acid peptizationtype titania (anatase form) sols (STS-02, average particle diameter 7nm, manufactured by Ishihara Sangyo Kaisha Ltd.; and ST-K01,manufactured by Ishihara Sangyo Kaisha Ltd.) and nitric acid peptizationtype titania (anatase form) sols (TA-15, average particle diameter 12nm, manufactured by Nissan Chemical Industries Ltd.).

A photocatalyst having a smaller particle diameter can more effectivelycauses the photocatalytic reaction and hence is preferred. Use of aphotocatalyst having an average particle diameter of preferably not morethan 50 nm, more preferably not more than 20 nm, is preferred. Further,the photocatalyst having a smaller particle diameter can advantageouslyprovide a photocatalyst-containing layer having smaller surfaceroughness. A surface roughness of the photocatalyst-containing layerexceeding 10 nm is unfavorable because the lowering in the waterrepellency and the oil repellency of the photocatalyst-containing layerin its unexposed areas is unsatisfactory.

According to the present invention, the binder used in thephotocatalyst-containing layer preferably has a binding energy highenough to avoid the decomposition of the main skeleton uponphotoexcitation of the photocatalyst, and example thereof include (1)organopolysiloxanes that hydrolyze and polycondensate a chloro- oralkoxysilane or the like by a sol-gel reaction or the like to developlarge strength and (2) organopolysiloxanes obtained by crosslinkingreactive silicones having excellent water repellency or oil repellency.

In the case of (1), the organopolysiloxane is composed mainly of ahydrolysis condensate or a cohydrolysis condensate of at least onemember selected from silicon compounds represented by general formulaY_(n)SiX_(4-n), wherein n is 1 to 3; Y represents an alkyl, fluoroalkyl,vinyl, amino, or epoxy group; and X represents a halogen or a methoxy,ethoxy, or acetyl group.

Specific examples thereof include methyltrichlorosilane,methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane,methyltriisopropoxysilane, methyl-tri-t-butoxysilane;ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane,ethyltriethoxysilane, ethyltriisopropoxysilane,ethyl-tri-t-butoxysilane; n-propyltrichlorosilane,n-propyltribromosilane, n-propyltrimethoxysilane,n-propyltriethoxysilane, n-propyltriisopropoxysilane,n-propyl-tri-t-butoxysilane; n-hexytrichlorosilane,n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane,n-hexyltriisopropoxysilane, n-hexyl-tri-t-butoxysilane;n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane,n-decyltriethoxysilane, n-decyltriisopropoxysilane,n-decyl-tri-t-butoxysilane; n-octadecyltrichlorosilane,n-octadecyltribromosilane, n-octadecyltrimethoxysilane,n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane,n-octadecyl-tri-t-butoxysilane; phenyltrichlorosilane,phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane,phenyltriisopropoxysilane, phenyl-tri-t-butoxysilane; tetrachlorosilane,tetrabromosilane, tetramethoxysilane, tetraethoxysilane,tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldichlorosilane,dimethyldibromosilane, di-methyldimethoxysilane, dimethyldiethoxysilane;diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane,diphenyldiethoxysilane; phenylmethyldichlorosilane,phenylmethyldibromosilane, phenylmethyldimethoxysilane,phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane,trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxyhydrosilane,ti-t-butoxyhydrosilane; vinyltrichlorosilane, vinyltribromosilane,vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane,vinyl-tri-t-butoxysilane; trifluoropropyltrichlorosilane,trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane,trifluoropropyltriethoxysilane, tifluoropropyltriisopropoxysilane,trifluoropropyl-tri-t-butoxysilane;γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropyltriisopropoxysilane,γ-glycidoxypropyl-tri-t-butoxysilane;γ-methacryloxypropylmethyldimethoxysilane,γ-methacryloxypropylmethyldiethoxysilane,γ-methacryloxypropyltrimethoxysilane,γ-methacryloxypropyltriethoxysilane,γ-methacryloxypropyltriisopropoxysilane,γ-methacryloxypropyl-tri-t-butoxysilane;γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropyltriisopropoxysilane, γ-aminopropyl-ti-t-butoxysilane;γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltliisopropoxysilane,γ-mercaptopropyl-tri-t-butoxysilane;β-(3,4-epoxycyclohexylethyltrimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltriethoxysilane; and partial hydrolyzatesthereof; aid mixtures thereof.

Further, polysiloxanes containing fluoroalkyl groups are particularlypreferred as the binder. Specific examples thereof include a hydrolysiscondensate or a cohydrolysis condensate of at least one member selectedfrom the following fluoroalkylsilanes. In general, polysiloxanes knownas fluorine silane coupling agents may be used.

-   -   CF₃(CF₂)₃CH₂CH₂Si(OCH₃)₃,    -   CF₃(CF₂)₅CH₂CH₂Si(OCH₃)₃,    -   CF₃(CF₂)₇CH₂CH₂Si(OCH₃)₃,    -   CF₃(CF₂)_(g)CH₂CH₂Si(OCH₃)₃,    -   (CF₃)₂CF(CF₂)₆CH₂ CH₂Si(OCH₃)₃,    -   (CF₃)₂CF(CF₂)₆CH₂ CH₂Si(OCH₃)₃,    -   (CF₃)₂CF(CF₂)₈CH₂ CH₂Si(OCH₃)₃,    -   CF₃(C₆H₄)C₂H₄Si(OCH₃)₃,    -   CF₃(CF₂)₃(C₆H₁)C₂H₂Si(OCH₃)₃,    -   CF₃(CF₂)₅(C₆H₁)C₂H₄Si(OCH₃)₃,    -   CF₃(CF₂)₇(C₆H₄)C₂H₄Si(OCH₃)₃,    -   CF₃(CF₂)₃CH₂CH₂SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₅CH₂CH₂SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₇CH₂CH₂SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)_(g)CH₂CH₂SiCH₃ (OCH₃)₂,    -   (CF₃)₂CF(CF₂)₄CH₂ CH₂SiCH₃ (OCH₃)₂,    -   (CF₃)₂CF(CF₂)₆CH₂ CH₂SiCH₃ (OCH₃)₂,    -   (CF₃)₂CF(CF₂)₈CH₂ CH₂SiCH₃ (OCH₃)₂,    -   CF₃(C₆H₄)C₂H₄SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₃(C₆H₄)C₂H₄SiCH₃(OCH₃)₂,    -   CF₃(CF₂)₅(C₆H₄)C₂H₄SiCH₃(OCH₃)₂,    -   CF₃(CF₂)₇(C₆H₄)C₂H₄SiCH₃(OCH₃)₂,    -   CF₃(CF₂)₃ CH₂ CH₂Si(OCH₂ CH₃)₃,    -   CF₃(CF₂)₅ CH₂ CH₂Si(OCH₂ CH₃)₃,    -   CF₃(CF₂)₇ CH₂ CH₂Si(OCH₂ CH₃)₃,    -   CF₃(CF₂)₉ CH₂ CH₂Si(OCH₂ CH₃)₃, and    -   CF₃(CF₂)₇SO₂N(C₂H₅)C₂H₄CH₂Si(OCH₃)₃.

Use of the polysiloxanes containing fluoroalkyl groups as the binderresults in markedly improved water repellency and oil repellency of thephotocatalyst-containing layer in its unexposed areas and can developthe function of inhibiting the deposition of the black matrixcomposition and the composition for a colored layer.

Examples of reactive silicones (2) include compounds having a skeletonrepresented by the following general formula B-1.

wherein n is an integer of two or more; and R¹ and R² represent asubstituted or unsubstituted allyl, alkenyl, aryl, or cyanoalkyl grouphaving 1 to 10 carbon atoms. Not more than 40% by mole of the whole isaccounted for by vinyl, phenyl, or phenyl halide. R¹ and R² preferablyrepresent a methyl group because the surface free energy of the siliconeis the smallest. The molar proportion of the methyl group is preferablynot less than 60%. Further, the chain end or the side chain has in itsmolecular chain at least one reactive group, such as a hydroxyl group.

A stable organosilicon compound not causing any crosslinking reaction,such as dimethylpolysiloxane, together with the organopolysiloxane, maybe incorporated into the binder.

According to the present invention, the photocatalyst-containing layermay comprise a surfactant in addition to the photocatalyst and thebinder. Specific examples of surfactants usable herein includehydrocarbon nonionic surfactants, such as NIKKOL BL, BC, BO, and BBseries manufactured by Nikko Chemicals Co., Ltd.; and fluoro or siliconenonionic surfactants, such as ZONYL FSN and FSO, manufactured by E.I. duPont de Nemours & Co., SurfluonS-141 and 145 manufactured by Asahi GlassCo., Ltd., Megafac F-141 and 144 manufactured by Dainippon Ink andChemicals, Inc., Ftergent F-200 and E-251, manufactured by Neos Co.,Ltd.; Unidyne DS-401 and 402 manufactured by Daikin Industries, Ltd.,and Fluorad FC-170 and 176 manufactured by Sumitomo-3M Ltd. Cationic,anionic, and amphoteric surfactants may also be used.

Further, besides the surfactant, the following compound may beincorporated into the photocatalyst-containing layer: oligomers andpolymers, such as polyvinyl alcohol, unsaturated polyesters, acrylicresins, polyethylene, diallyl phthalate, ethylene propylene dienemonomer, epoxy resin, phenolic resin, polyurethane, melamine resin,polycarbonate, polyvinyl chloride, polyamide, polyimide, styrenebutadiene rubber, chloroprene rubber, polypropylene, polybutylene,polystyrene, polyvinyl acetate, polyester, polybutadiene,polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, andpolyisoprene.

The photocatalyst-containing layer 203, 213, 223, or 233 constitutingthe color filter 201, 211, 221, or 231 may be formed by dispersing aphotocatalyst, a binder and optionally other additives in a solvent toprepare a coating liquid and coating the coating liquid. Preferredsolvents usable herein include alcoholic organic solvents, such asethanol and isopropanol. The coating liquid may be coated by aconventional coating method such as spin coating, spray coating, dipcoating, roll coating, or bead coating. When the coating liquid containsan ultraviolet curable component as the binder, thephotocatalyst-containing layer may be formed by curing throughultraviolet irradiation.

The content of the photocatalyst in the photocatalyst-containing layermay be generally 5 to 60% by weight, preferably 20 to 40% by weight. Thethickness of the photocatalyst-containing layer is preferably not morethan 10 μm.

According to the present invention, besides the photocatalyst-containinglayer, an organic polymeric resin layer may be used as thewettability-variable component layer for color filter 201, 211, 221, or231. Organic polymers, such as polycarbonate, polyethylene, polyethyleneterephthalate, polyamide, and polystyrene, when exposed to ultravioletlight, particularly exposed to ultraviolet light containing a largeamount of a component of low wavelengths of not more than 250 nm, causecleavage of polymer chains to reduce the molecular weight. This createssurface roughening to change the wettability and hence brings theexposed areas to a high critical surface tension state. This phenomenoncan be utilized to create a large difference in wettability betweenexposed areas and unexposed areas, thereby enhancing the receptivity andrepellency to the composition for a light shielding layer and thecomposition for a colored layer to obtain a color filter. As describedabove, the high critical surface tension refers to a state of preferablynot more than 40°, more preferably not more than 10°, in terms ofcontact angle with water.

(Black Matrix)

The black matrixes 204 and 234 constituting the color filters 201 and231 are formed respectively on the photocatalyst-containing layer 203 inits high critical surface tension areas and the firstphotocatalyst-containing layer 233 a in its high critical surfacetension areas and are located at each boundary region between displaypixels of colored layers 205 and 235 and outside the colored layerformation regions. The black matrix 204 or 234 comprises a resin bindercontaining fine particles of carbon, a metal oxide, an inorganicpigment, an organic pigment or the like. The thickness of the blackmatrix may be in the range of 0.5 to 10 μm. The resin binder maycomprise one aqueous resin or a mixture of two or more aqueous resinsselected from polyacrylamide, polyvinyl alcohol, gelatin, casein,cellulose and the like. Further, an o/w emulsion type resin composition,for example, an emulsion of a reactive silicone, may also be used as theresin binder.

The black matrix 214 or 224 constituting the color filter 211 or 221 isprovided at each boundary region between display pixels of the colorlayer 215 or 225 and outside the colored layer formation regions. Theblack matrix 214 or 224 may be formed by forming an about 1000 to 2000Å-thick thin metal film of chromium or the like by sputtering, vacuumdeposition or the like and patterning the thin film, by forming a resinlayer of a polyimide resin, an acrylic resin, an epoxy resin or the likecontaining light shielding particles, such as fine particles of carbon,and patterning the resin layer, by forming a photosensitive resin layercontaining light shielding particles, such as fine particles of carbonor a metal oxide, and patterning the photosensitive resin layer, or byother method.

(Colored Layer)

The colored layer 205, 215, 225 or 235 is provided on thephotocatalyst-containing layer in its high critical surface tensionareas, and a red pattern, a green pattern, and a blue pattern arearranged in a desired pattern form. The colored layer comprises a layerof a colorant, such as an inorganic pigment, an organic pigment, or adye, or comprises a layer of a binder containing the colorant. The resinbinder may be one aqueous resin or a mixture of two or more aqueousresins selected from polyacrylamide, polyvinyl alcohol, gelatin, casein,cellulose and the like. An o/w emulsion type resin composition, forexample, an emulsion of a reactive silicone, may also be used as theresin binder.

The red pattern, the green pattern, and the blue pattern constitutingthe colored layer may be arranged in any conventional form of stripe,mosaic, triangle, four pixel disposition and the like.

(Protective Layer)

The protective layer 206, 216, 226 or 236 functions to flatten thesurface of the color filter and to prevent the elution of the coloredlayer or the components contained in the colored layer and thephotocatalyst-containing layer into a liquid crystal layer. Thethickness of the protective layer may be determined by taking intoconsideration the light transmission of the material used, the surfacestate of the color filter and the like, for example, may be in the rangeof 0.1 to 2.0 μm. The protective layer may be formed using a materialselected from, for example, conventional transparent photosensitiveresins, two-component curable transparent resins and the like that havelight transmittance and the like required of the transparent protectivelayer.

Process for Producing Color Filter According to Present Invention FIRSTEMBODIMENT

Next, an embodiment of the process for producing a color filteraccording to the present invention will be described by taking a colorfilter 201 shown in FIG. 13 as an example with reference to FIG. 17.

(First Step)

In the first step, a photocatalyst-containing layer 203 as awettability-variable component layer is formed on a transparentsubstrate 202 (FIG. 17 (A)). The photocatalyst-containing layer 203 maybe formed by dispersing the photocatalyst, the binder, and optionallyother additives in a solvent to prepare a coating liquid, coating thecoating liquid, and allowing hydrolysis and polycondensation to proceedto strongly fix the photocatalyst in the binder. Preferred solventsusable herein include alcoholic organic solvents, such as ethanol andisopropanol. The coating liquid may be coated by a conventional coatingmethod, such as spin coating, spray coating, dip coating, roll coating,or bead coating.

Next, the photocatalyst-containing layer 203 in its black matrix formingareas are exposed to light to bring light exposed areas 203′ to a highcritical surface tension state through photocatalytic action. Thus,areas having specific wettability are formed (FIG. 17 (B)). Thisexposure to light may be pattern-wise exposure by means of a mercurylamp, a metal halide lamp, a xenon lamp or the like through a photomaskfor a black matrix. Alternatively, a laser, such as an excimer laser ora YAG laser, may be applied to directly form a pattern of the blackmatrix. The wavelength of the light used in this light irradiation maybe generally not more than 400 nm, preferably not more than 380 nm. Theexposure in the light irradiation may be one that is necessary for thelight exposed areas 203′ to develop high critical surface tension (forexample, a water contact angle of not more than 10°).

A coating composition for the black matrix is then deposited on thelight exposed areas 203′ and cured to form a black matrix 204 (FIG. 17(C)). The black matrix composition may be deposited on the exposed areas203′ by coating the coating composition onto thephotocatalyst-containing layer 203 according to a conventional coatingmethod, such as spray coating, dip coating, roll coating, or beadcoating. In this case, the coating composition is repelled by theunexposed areas having low critical surface tension and removed, so thatthe coating composition is selectively deposited only onto the exposedareas having high critical surface tension (areas having specificwettability) 203′. Alternatively, the black matrix composition may bedeposited onto the exposed areas 203′ by a nozzle ejection method, suchas ink jetting. In this case, the black matrix composition fed into theexposed areas 203′ through the nozzle ejection is homogeneously diffusedand deposited in the exposed areas 203′ showing high critical surfacetension, whereas the black matrix composition are not diffused in theunexposed areas having low critical surface tension. In this case, eventhough the coating composition fed by the nozzle ejection overflows fromthe exposed areas 203′, the overflowed composition is repelled by theunexposed areas having low critical surface tension and finallydeposited within the exposed areas 203′.

Further, the formation of the black matrix 204 may be carried out byfilm formation utilizing vacuum. Specifically, the black matrix 204 maybe formed by a method which comprises forming a thin metal film on theexposed photocatalyst-containing layer 203 by vapor deposition or thelike and patterning the thin metal film utilizing a difference inadhesion between the unexposed areas and the exposed areas 203′, thatis, by separation using a pressure-sensitive adhesive tape, by solventtreatment or by other method.

(Second Step)

Next, red pattern 205R forming areas on the photocatalyst-containinglayer 203 are exposed to light to bring exposed areas 203′ to a highcritical surface tension state through photocatalytic action to formareas having specific wettability (FIG. 17 (D)). As with the lightirradiation in the step of forming the black matrix (first step), thislight irradiation may be any of pattern-wise exposure and light beamexposure. A coating composition for a red pattern is fed to thephotocatalyst-containing layer 203. As with the feed of the coatingcomposition in the step of forming the black matrix (first step), thecoating composition for a red pattern may be fed by a coating method, anozzle ejection method, such as ink jetting, a film formation methodutilizing vacuum or the like. The coating composition fed to thephotocatalyst-containing layer is repelled by the black matrix 204 andthe unexposed areas having low critical surface tension and removed, sothat the coating composition is selectively deposited only onto theexposed areas 203′ having high critical surface tension. The coatingcomposition for a red pattern deposited onto the exposed areas 203′ iscured to form a red pattern 205R (FIG. 17 (E)). When the red pattern205R is formed by the film formulation method utilizing vacuum, a thinfilm of the coating composition for a red pattern is formed on theexposed photocatalyst-containing layer 203 by vapor deposition or thelike, followed by patterning of the thin film utilizing a difference inadhesion between the unexposed areas and the exposed areas 203′, thatis, by separation using a pressure-sensitive adhesive tape, by solventtreatment or by other method, to form a red pattern 205P.

The same procedure as used in the formation of a red pattern is repeatedto form a green pattern 205G and a blue pattern 205B. Thus, a coloredlayer 205 comprising a red pattern, a green pattern, and a blue patternis formed. A protective layer 206 is formed on the colored layer 205 toobtain a color filter 201 shown in FIG. 13 (FIG. 17 (F)).

When the nozzle ejection method is used in the second step and eachcolor pattern (pixel) is surrounded by the black matrix 204, it ispossible to form a colored layer by a method which comprises applyinglight to the whole areas of the photocatalyst-containing layer 203 withthe black matrix 204 formed thereon in the first step to bring the wholearea of the photocatalyst-containing layer to a high critical surfacetension through photocatalytic action and feeding and homogeneouslydiffusing and depositing a coating composition for a color pattern ontothe pattern forming areas for each color through a nozzle, followed bycuring to form a colored layer.

When an organic polymeric resin layer is used as thewettability-variable component layer, light irradiation is carried outusing ultraviolet light containing a large amount of a component of lowwavelengths of not more than 250 nm.

SECOND EMBODIMENT

Next, the second embodiment of the process for producing a color filteraccording to the present invention will be described by taking a colorfilter 211 shown in FIG. 14 as an example with reference to FIG. 18.

(First Step)

In the first step, a photocatalyst-containing layer 213 is formed on atransparent substrate 212 with a black matrix 214 previously formedthereon (FIG. 18 (A)). The photocatalyst-containing layer 213 may beformed in the same manner as used in the formation of thephotocatalyst-containing layer in the first embodiment.

Next, the photocatalyst-containing layer 213 in its red pattern formingareas are exposed to light to bring light exposed areas 213′ to a highcritical surface tension state through photocatalytic action. Thus,areas having specific wettability are formed (FIG. 18 (B)). As with thelight irradiation in the step of forming a black matrix (first step) inthe first embodiment, the light irradiation may be pattern-wise exposureor light beam exposure.

(Second Step)

Next, a coating composition for a red pattern is fed to thephotocatalyst-containing layer 213. As with the feed of the coatingcomposition in the step of forming the black matrix (first step) in thefirst embodiment, the coating composition for a red pattern may be fedby a coating method, a nozzle ejection method, such as ink jetting, afilm formation method utilizing vacuum or the like. The coatingcomposition fed to the photocatalyst-containing layer is repelled by theunexposed areas having low critical surface tension and removed, so thatthe coating composition is selectively deposited only onto the exposedareas 213′ having high critical surface tension. The coating compositionfor a red pattern deposited onto the exposed areas 213′ is cured to forma red pattern 215R (FIG. 18 (C)).

The same procedure as used in the formation of the red pattern isrepeated to form a green pattern 215G and a blue pattern 215B. Thus, acolored layer 215 comprising a red pattern, a green pattern, and a bluepattern is formed. A protective layer 216 is formed on the colored layer215 to obtain a color filter 211 shown in FIG. 14 (FIG. 18 (D)).

When the nozzle ejection method is used in the second step and a patternof the black matrix 214 is formed so as to surround each color pattern(pixel), it is possible to form a colored layer by a method whichcomprises applying light to the whole area of thephotocatalyst-containing layer 213 formed on the transparent substrate212 in the first step so as to cover the black matrix 214 through a maskM, as shown in FIG. 19, having a light shielding pattern (a hatchedregion shown in FIG. 19) of which the line width (w) is smaller than theline with (W) of the black matrix 214, thereby bringing the whole areaof the photocatalyst-containing layer to a high critical surface tensionstate through photocatalytic action, and, thereafter, feeding andhomogeneously diffusing and depositing a coating composition for a colorpattern onto the pattern forming areas for each color through a nozzle,followed by curing to form a colored layer.

When an organic polymeric resin layer is used as thewettability-variable component layer, light irradiation is carried outusing ultraviolet light containing a large amount of a component of lowwavelengths of not more than 250 nm.

THIRD EMBODIMENT

Next, the third embodiment of the process for producing a color filteraccording to the present invention still be described by taking a colorfilter 221 shown in FIG. 15 as an example with reference to FIG. 20.

At the outset, a first photocatalyst-containing layer 223 a is formed ona transparent substrate 222 with a black matrix 224 previously formedthereon. Next, the photocatalyst-containing layer 223 a in its redpattern forming areas are exposed to light to bring light exposed areas223′a to a high critical surface tension state through photocatalyticaction. Thus, areas having specific wettability are formed (FIG. 20(A)). The first photocatalyst-containing layer 223 a may be formed inthe same manner as used in the formation of the photocatalyst-containinglayer 203 in the first embodiment. As with the light irradiation in thestep of forming a black matrix (first step) in the first embodiment, theexposure of the first photocatalyst-containing layer 223 a to light maybe pattern-wise exposure or light beam exposure. Next, a coatingcomposition for a red pattern is fed to the firstphotocatalyst-containing layer 223 a. As with the feed of the coatingcomposition in the step of forming the black matrix (first step) in thefirst embodiment, the coating composition for a red pattern may be fedby a coating method, a nozzle ejection method, such as ink jetting, afilm formation method utilizing vacuum or the like. The coatingcomposition fed to the first photocatalyst-containing layer is repelledby the unexposed areas having low critical surface tension and removed,so that the coating composition is selectively deposited only onto theexposed areas 223′a having high critical surface tension. The coatingcomposition for a red pattern deposited onto the exposed areas 223′a iscured to form a red pattern 225R (FIG. 20 (B)). Thus, a laminatecomprising a first photocatalyst-containing layer 223 a and a redpattern 225R formed on the photocatalyst-containing layer 223 a in itsexposed areas (high critical surface tension areas) 223′a is formed onthe transparent substrate 222.

In the same manner as used in the formation of the red pattern, a secondphotocatalyst-containing layer 223 b is formed. Thephotocatalyst-containing layer 223 b on its green pattern 225G formingareas is exposed to light to bring exposed areas 223′b to a highcritical surface tension state through photocatalytic action. Thus,areas having specific wettability are formed (FIG. 20 (C)). A coatingcomposition for a green pattern is deposited onto the exposed areas223′b, following by curing to form a green pattern 225G (FIG. 20 (D)).Thus, a laminate comprising a second photocatalyst-containing layer 223b and a green pattern 225G formed on the photocatalyst-containing layer223 b in its exposed areas (high critical surface tension areas) 223′bis formed on the transparent substrate 222.

The above procedure is repeated to form, on the transparent substrate222, a laminate comprising a third photocatalyst-containing layer 223 cand a blue pattern 225B formed on the photocatalyst-containing layer 223c in its exposed areas (high critical surface tension areas) 223′c.Thus, a colored layer 225 comprising a red pattern, a green pattern, anda blue pattern is formed. A protective layer 226 is formed on thecolored layer 225 to obtain a color filter 221 shown in FIG. 15 (FIG. 20(E)).

When an organic polymeric resin layer is used as thewettability-variable component layer, the light irradiation is carriedout using ultraviolet light containing a large amount of a component oflow wavelengths of not more than 250 nm.

FOURTH EMBODIMENT

Next, the fourth embodiment of the process for producing a color filteraccording to the present invention will be described by taking a colorfilter 231 shown in FIG. 16 as an example with reference to FIG. 21.

(First Step)

In the first step, a first photocatalyst-containing layer 233 a isformed on a transparent substrate 232. The photocatalyst-containinglayer 233 a on its black matrix forming areas is exposed to light tobring exposed areas 233′a to a high critical surface tension statethrough photocatalytic action. Thus, areas having specific wettabilityare formed (FIG. 21(A)). The first photocatalyst-containing layer 233 amay be formed in the same manner as used in the formation of thephotocatalyst-containing layer 203 in the first embodiment As with thelight irradiation in the step of forming a black matrix (second step) inthe first embodiment, the exposure of the first photocatalyst-containinglayer 233 a to light may be pattern-wise exposure or light beamexposure.

Next, a coating composition for a black matrix is deposited on theexposed areas 233′a, followed by curing to form a black matrix 234 (FIG.21 (B)). As with the deposition of the black matrix composition in thestep of forming a back matrix (first step) in the first embodiment, thedeposition of the black matrix composition onto the exposed areas 233′amay be carried out by a coating method, a nozzle ejection method, suchas ink jetting, a film formation method utilizing vacuum or the like.

(Second Step)

A second photocatalyst-containing layer 233 b is formed onto the firstcatalyst-containing layer 233 a so as to cover the black matrix 234formed on the first step. The photocatalyst-containing layer 233 b onits red pattern forming areas is exposed to light to bring exposed areas233′b to a high critical surface tension state through photocatalyticaction. Thus, areas having specific wettability are formed (FIG. 21(C)). The second photocatalyst-contain ng layer 233 a may be formed inthe same manner as used in the formation of the firstphotocatalyst-containing layer 233 a. As with the exposure of the firstphotocatalyst-containing layer 233 a to light, the exposure of thesecond photocatalyst-containing layer 233 b to light may be pattern-wiseexposure or light beam exposure. Subsequently, a coating composition fora red pattern is fed to the second photocatalyst-containing layer 233 b.As with the feed of the coating composition in the step of forming ablack matrix (second step) in the first embodiment, the feed of thecoating composition for a red pattern may be fed by a coating method, anozzle ejection method, such as ink jetting, a film formation methodutilizing vacuum or the like. The coating composition fed to thephotocatalyst-containing layer is repelled by the black matrix 234 andthe unexposed areas having low critical surface tension and removed, sothat the coating composition is selectively deposited only onto theexposed areas 233′b having high critical surface tension. The coatingcomposition for a red pattern deposited onto the exposed areas 233′b iscured to form a red pattern 235R (FIG. 21 (D)). Thus, a laminatecomprising a second catalyst-containing layer 233 b and a red pattern235R formed on the photocatalyst-containing layer 233 b in its exposedareas (high critical surface tension areas) 233′b is formed on the firstphotocatalyst-containing layer 233 a.

The same procedure is repeated to form, on the secondphotocatalyst-containing layer 233 b, a laminate comprising a thirdphotocatalyst-containing layer 233 c and a green pattern 235G formed onthe photocatalyst-containing layer 233 c in its exposed areas (highcritical surface tension areas) 233′c. Further, a laminate comprising afourth photocatalyst-containing layer 233 d and a blue pattern 235Bformed on the photocatalyst-containing layer 233 d in its exposed areas(high critical surface tension areas) 233′d is formed on the thirdphotocatalyst-containing layer 233 c. Thus, a colored layer 235comprising a red pattern, a green pattern, and a blue pattern is formed.A protective layer 236 is formed on the colored layer 235 to obtain acolor filter 231 shown in FIG. 16 (FIG. 21 (E)).

As described above, according to the present invention, the compositionfor a black matrix and the composition for a colored layer can bedeposited selectively onto the black matrix or colored layer formingareas. Therefore, the coating composition can be very efficientlyutilized.

When an organic polymeric resin layer is used as thewettability-variable component layer, the light irradiation is carriedout using ultraviolet light containing a large amount of a component oflow wavelengths of not more than 250 nm.

In the above embodiments of the color filter and the process forproducing a color filter, the number of colors and position of thecolored layer and the like are illustrative only and are not intended tolimit the present invention.

Re: Third Invention C

Pattern Based on Difference in Wettability

(Wettability)

The substrate used in the present invention has on its surface areasdifferent from each other in wettability, that is, areas on which aliquid containing a lens forming material (hereinafter referred to alsoas “lens composition”) is depositable and areas on which the lenscomposition is undepositable. The numerical value of the wettability isnot particularly limited so far as the surface of the substrate hasareas different from each other in wettability. The surface having areasdifferent from each other in wettability may be the surface of thesubstrate per se or the substrate surface after surface treatment suchas dampening water treatment.

In the present invention, the wettability may be evaluated, for example,by the contact angle of the surface with a liquid containing only adispersion force component, such as a saturated hydrocarbon liquid, aliquid having a hydrogen bond, such as water, or a liquid containing adispersion force component and a polar component, such as methyleneiodide, or by surface free energy of the solid surface or the criticalsurface tension of the solid surface. Although no particular limitationis imposed, the wettability of the substrate used in the presentinvention may be, for example, not less than 70 dyne/cm for areas havinghigher wettability and, for example, not more than 30 dyne/cm for areashaving lower wettability.

(Wettability Variation Method)

Methods for varying the wettability of the surface of the substrate toform a pattern include, but are not limited to, a method wherein thesurface of the substrate is modified, a method wherein a film havingdifferent wettability is partially formed on the surface of thesubstrate, a method wherein a film on the surface of the substrate ispartially removed to form areas having different wettability, and amethod wherein a film is formed on the whole surface of the substratefollowed by partial modification of the film.

Among them, a preferred method is to form a film on the whole surface ofthe substrate followed by partial modification of the film. Inparticular, the formation of a photocatalyst-containing layer, of whichthe wettability is variable upon light irradiation on the whole surfaceof the substrate, followed by light irradiation to form a pattern ismore advantageous, for example, in that development is unnecessary, nowaste is produced in the transfer or removal at the time of patternformation, areas having different wettability can be formed withoutproviding a large difference in level, and the material is inexpensive.Further, microlenses can be mass produced with high accuracy.

(Form of Pattern)

A composition for a lens may be deposited onto either thewettability-varied areas or the wettability-unvaried areas, and the formof the pattern is not particularly limited so far as lenses can beformed. Preferably, the pattern for the lens composition deposited maybe in any of square, circle, regular hexagon and the like.

The number of areas on which the lens composition are to be deposited isnot limited. Preferably, a large number of deposited areas are orderlyprovided.

The size of the pattern may be properly designed according toapplications. The process for producing a lens according to the presentinvention also features the formation of fine microlenses. For example,microlenses having a very small diameter of, for example, 2 μm can beproduced.

Although the area ratio of the lens composition-deposited region to thelens composition-undeposited region is not limited, it may be, forexample, 10000:1 to 1:10000.

(Lens Forming Material)

Materials for the lens of the present invention are not particularlylimited so far as they are transparent materials that, after depositionas a liquid onto a substrate, can be cured and, after curing, canfunction as a lens according to applications.

Examples of materials usable for the lens of the present inventioninclude combinations of photocurable resins with photopolymerizationinitiators, and thermosetting resins. Among them, photocurable resins,such as ultraviolet curable resins, are preferred because they can beeasily and rapidly cured and the temperature of the lens formingmaterial and the substrate does not become high at the time of curing.

When the material is colored with a colorant to prepare a color lenshaving the function of a color filter, colorants usable herein includedyes, inorganic pigments, and organic pigments.

More specific examples of materials usable for lenses are as follows.

(1) Photocurable Resin Composition

Photocurable resin compositions which may be preferably used in thepresent invention are highly transparent to visible light. Thephotocurable resin composition refers to a monomer or an oligomer thathas at least one functional group and is ionically polymerized orradically polymerized by ions or radical generated upon application of acuring energy radiation to a photopolymerization initiator to increasethe molecular weight or to form a crosslinked structure. The functionalgroup refers to an atomic group or a bonding form causative of reactionsof vinyl, carboxyl, or hydroxyl groups.

Monomers and oligomers usable herein include unsaturated polyester,enethiol, acrylic and other monomers and oligomers. Among them, acrylicmonomers and oligomers are preferred from the viewpoints of curing speedand the range of selectable properties. Representative examples ofacrylic monomers and oligomers usable herein include the followingcompounds.

(1-1) Monofunctional Compounds

2-Ethylhexyl acrylate, 2-ethylhexyl EO adduct acrylate, ethoxydiethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropylacrylate, caprolactone adduct of 2-hydroxyethyl acrylate, 2-phenoxyethylacrylate, phenoxydiethylene glycol acrylate, nonyl phenol EO adductacrylate, acrylate which has been caprolactone added to nonyl phenol EOadduct, 2-hydroxy-3-phenoxypropyl acrylate, tetrahydrofurfuryl acrylate,furfuryl alcohol caprolactone adduct acrylate, acryloylmorpholine,dicyclopentenyl acrylate, dicyclopentanyl acrylate,dicyclopentenyloxyethyl acrylate, isobornyl acrylate,4,4-dimethyl-1,3-dioxolane caprolactone adduct acrylate, and3-methyl-5,5-dimethyl-1,3-dioxolane caprolactone adduct acrylate.

(1-2) Polyfunctional Compounds

Hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycoldiacrylate, tripropylene glycol diacrylate, hydroxypivalic acidneopentyl glycol ester diacrylate, hydroxypivalic acid neopentyl glycolester caprolactone adduct diacrylate, acrylic acid adduct of1,6-hexanediol diglycidyl ether, diacrylate of acetal compound ofhydroxypivalaldehyde with trimethylolpropane,2,2-bis[4-(acryloyloxydiethoxy)phenyl]propane,2,2-bis[4-(acryloyloxydiethoxy)phenyl]methane, hydrogenated bisphenolethylene oxide adduct diacrylate, tricyclodecane dimethanol diacrylate,trimethylolpropane triacrylate, pentaerythritol triacrylate,trimethylolpropane propylene oxide adduct triacrylate, glycerinpropylene oxide adduct triacrylate, mixture of dipentaerythritolhexaacrylate with pentaacrylate, dipentaerythritol caprolactone adductacrylate, tris(acryloyloxyethyl)isocyanurate, 2-acryloyloxyethylphosphate and the like.

(2) Photopolymerization Initiator

The photopolymerization initiator used in the present invention is notparticularly limited and may be selected from conventionalpolymerization initiators. Representative examples ofphotopolymerization initiators usable herein include the followingcompounds.

(2-1) Carbonyl Compounds

Acetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoinether, benzyl dimethyl ketal, benzoin benzoate, α-acyloxime ester andthe like.

(2-2) Sulfur Compounds

Tetramethylthiuram monosulfide, thioxanthones and the like.

(2-3) phosphorus compounds

2,4,6-Trimethylbenzoyl diphenylphosphinoxide and the like

(3) Thermoplastic Resin Composition

Thermoplastic resin compositions having high transparency to visiblelight region. Preferred are thermoplastic resin compositions that areexcellent in transparency, as well as in optical properties, such asrefractive index, dispersion properties, and birefringence.Representative examples of thermoplastic resin compositions usableherein include homopolymers or copolymers of polycarbonate, polymethylmethacrylate, and methyl phthalate, polyethylene terephthalate,polystyrene, diethylene glycol bisallyl carbonate, acrylonitrile/styrenecopolymer, methyl methacrylate styrene copolymer, andpoly(-4-methylpentene-1).

(4) Colorant

In the lens according to the present invention, dissolution of a dye ina material for a lens, dispersion of a pigment in the material for alens or the like to color the material can provide a color lens. Thecolorant usable in the present invention may be any of a dye, an organicpigment and an inorganic pigment which are commonly used in colorfilters. Among them, materials are preferred which can provide highcolor density and are less likely to cause fading at the time of curingof the lens and in use, and examples thereof are as follows:

dyes, for example, azo dyes, anthraquinone dyes, indigoid dyes,phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes,quinoline dyes, nitro dyes, benzoquinone dyes, naphthoquinone dyes,naphthalimide dyes, perinone dyes, pyrylium dyes, thiopyrylium dyes,azulenium dyes, and squarylium salt dyes, and organic pigments, forexample, dianthraquinone, copper halogenide phthalocyanine, copperphthalocyanine, and other phthalocyanine pigments, polycyclic quinonepigments, such as perylene pigments and pyranthrone pigments, indigopigments, quinacridone pigments, pyrrole pigments, pyrrolopyrrolepigments, and azo pigments. Other dyes and pigments may also be used sofar as they can satisfy colorant requirements. Further, the colorantsmay be used in any combination of two or more in any desired ratio sofar as there are no other limitations.

(Composition for Lens)

The composition for a lens is not particularly limited so far as thecomposition contains materials for the lens.

Compositions for a lens include a liquid comprising a monomer and apolymerization initiator, a solution or a dispersion of a monomer and apolymerization initiator, a liquid comprising an oligomer and apolymerization initiator, a solution or a dispersion of an oligomer anda polymerization initiator, and a solution or a dispersion of a monomer,an oligomer, and a polymerization initiator.

A material liquid for a color lens may be a solution or a dispersionprepared by dissolving or dispersing a colorant in the above materialliquid.

(Areas on Which Composition for Lens is to be Deposited)

In the process for producing a lens according to the present invention,the composition for a lens may be deposited onto any area of a patternbased on a difference in wettability on the surface of a substrate. Inother words, the composition may be deposited onto the surface of thesubstrate in its wettability-varied areas or wettability-unvaried areas.In one specific example thereof, the composition may be deposited ontohigh wettability areas or high critical surface tension areas, oralternatively may be deposited onto low wettability areas or lowcritical surface tension areas. When the composition for a lens isdeposited onto the low critical surface tension areas, preferably, thehigh critical surface tension areas are previously coated with dampeningwater, followed by deposition of the composition for a lens onto the lowcritical surface tension areas while avoiding direct contact of the lenscomposition with the high critical surface tension areas.

(Adjustment of Focal Length of Lens)

One of great features of the process for producing a lens according tothe present invention is that the adjustment of the focal length of thelens, that is, varying the curvature, can be very easily performed.

A specific example of the adjustment of the focal length of the lensaccording to the present invention will be described with reference toFIG. 22. A photocatalyst-containing layer 303 having low wettability bythe composition for a lens is provided on a transparent substrate 301. Apart of the photocatalyst-containing layer 303 constitutes awettability-varied photocatalyst-containing layer having highwettability by the composition for a lens and corresponding to areas onwhich the composition for a lens is to be deposited (hereinafterreferred to also as “modified photocatalyst-containing layer 303”).Further, a composition 302 for a lens is deposited on the modifiedphotocatalyst-containing layer 303′. FIG. 22 (A) shows an embodimentwherein a small amount of the composition 302 for a lens has beendeposited. Even when the amount of the composition 302 for a lens issmall, the composition is spread over the whole modifiedphotocatalyst-containing layer 303′, making it possible to formmicrolenses having small curvature and long focal length. FIG. 22 (B)shows an embodiment wherein a medium amount of the composition for alens has been deposited. As compared with FIG. 22 (A), microlenseshaving larger curvature and shorter focal length are formed. FIG. 22 (C)shows an embodiment wherein a large amount of the composition for a lenshas been deposited. Although the amount of the composition 302 for alens is large, the composition is not spread on thephotocatalyst-containing layer 303 having low wettability. As a result,microlenses having high curvature and short focal length are formed.

Thus, the process for producing a lens according to the presentinvention has an advantage that the focal length of the microlens can besimply regulated by varying the amount of the composition for a lensdeposited per place. Further, since the size of the bottom is specifiedby the size of the pattern, advantageously, a change in amount of thecomposition for a lens does not results in a change in the size of thebottom. Furthermore, even though the composition for a lens is depositedon a position slightly deviated from an originally predeterminedposition, the difference in wettability permits the position of thecomposition for a lens to be corrected to the position of the pattern.Therefore, a microlens array having very high positional accuracy can beadvantageously produced.

(Deposition of Composition for Lens by Coating)

In the process for producing a lens according to the present invention,the composition for a lens may be deposited by coating onto the surfaceof the substrate. Specific examples of coating methods usable hereininclude dip coating, roll coating, bead coating, spin coating, airdoctor coating, blade coating, knife coating, rod coating, gravurecoating, rotary screen coating, kiss coating, slot orifice coating,spray coating, cast coating, and extrusion coating. These coatingmethods are advantageous in that a large amount of lens shapes can beprepared in short time.

An array of lenses of a plurality of colors may be produced byrepeating, one color by one color as many times as required for thenecessary number of colors, the step of forming a pattern based on adifference in wettability on the surface of the substrate, the step ofdepositing the colored composition for a lens by the coating method asdescribed above, and optionally the step of curing the composition for alens.

(Deposition of Composition for Lens by Ejection Through Nozzle)

In the process for producing a lens according to the present invention,the composition for a lens can be deposited onto the surface of thesubstrate by ejection through a nozzle. Specific examples of ejectionmethods usable herein include ejection using microsyringe, ejectionusing a dispenser, ink jetting, a method wherein the composition for alens is ejected from a needle by external stimulation, such as anelectric field, a method wherein the composition for a lens is ejectedfrom a vibrating element, such as piezo element, which is vibrated byexternal stimulation, and a method wherein a composition for a lensdeposited on a needle is deposited on the surface of the substrate.These methods are advantageous in that lens shapes having a largecontact angle and large height can be prepared.

When an array of lenses of a plurality of colors is produced, nozzles inthe necessary number of colors as described above are used, and coloredcompositions for a lens containing materials for lenses of respectivecolors are ejected through respective nozzles and deposited onto thesurface of the substrate.

When an array of lenses of a plurality of colors is produced through anozzle for a single color, the array of color lenses may be produced byrepeating, one color by one color as many times as required for thenecessary number of colors, the step of forming a pattern based on adifference in wettability on the surface of the substrate, the step ofdepositing the colored composition for a lens by ejection through thenozzle as described above, and optionally the step of curing thecomposition for a lens.

(Microlens Array)

In the process for producing a lens according to the present invention,preferably, microlenses are orderly arranged to produce a microlensarray. The sequence of the microlens array correspond to the patternbased on a difference in wettability, and the shape of the bottom of themicrolens also corresponds to the pattern based on a difference inwettability. Therefore, the position and shape of the microlensesaccording to a preferred embodiment of the present invention are high.Further, the accuracy of the composition for a lens can be depositedonly onto areas having high wettability. In this case, the contact ismore intimate, and, hence, microlenses having higher strength can beproduced. The contact surface can be designed to be not only circularbut also polygonal. Therefore, as compared with circular lenses, thearea of other portions than the lens shape can be reduced, making itpossible to easily produce an array of microlenses having a highnumerical aperture.

Further, deposition of the colored composition for a lens can provide,as with the above microlenses, an array of color microlenses having highpositional and shape accuracy, high adhesion and strength, and highnumerical aperture can be easily produced.

FIG. 23 is a cross-sectional view of a microlens array according to apreferred embodiment of the present invention. The microlens arraycomprises: a substrate 301 having thereon a photocatalyst-containinglayer 303 and a wettability-varied modified photocatalyst-containinglayer 303′; and lenses 302 provided on the unmodifiedphotocatalyst-containing layer 303.

FIG. 24 is a cross-sectional view of a color microlens array accordingto a preferred embodiment of the present invention. The color microlensarray comprises: a substrate 301 having thereon aphotocatalyst-containing layer 303 and a wettability-varied modifiedphotocatalyst-containing layer 303′; and a first color lens 315, asecond color lens 316, and a third color lens 317 provided on theunmodified photocatalyst-containing layer 303.

Substrate

For the material constituting the substrate, a pattern based on adifference in wettability may be formed on the surface thereof either initself or by forming a layer. The material is not particularly limitedso far as it may form microlenses. When the material for the substrateis transparent and the transparent material is used, there is no need toprovide the step of removing the lenses from the substrate. This is veryeffective in producing a microlens array. Materials for the abovesubstrate are not particularly limited and may be inorganic or organicmaterials so far as they are commonly used in the production ofmicrolens arrays. Preferred examples thereof include soda glass, quartzglass, optical glass (BSC7, manufactured by HOYA), glass for electronics(such as alkali-free glass), translucent ceramics, plastic films andsheets of polycarbonate, methyl methacrylate homopolymer or copolymer,polyethylene terephthalate, and polystyrene.

The shape and thickness of the substrate may be varied depending-uponapplications, and the substrate may be in any fold commonly used in theart.

Photocatalyst-containing Layer

(Principle of Variation in Wettability)

According to a preferred embodiment of the present invention, aphotocatalyst capable of creating a chemical change in materials (suchas a binder) around it upon light irradiation may be used to form apattern based on a difference in wettability on light exposed areas. Themechanism of the action of the photocatalyst typified by titanium oxideaccording to a preferred embodiment of the present invention has notbeen fully elucidated. However, it is considered that carriers producedin the photocatalyst upon light irradiation directly change the chemicalstructure of the binder and the like, or otherwise active oxygen speciesproduced in the presence of oxygen and water changes the chemicalstructure of the binder and the like. Thus, the wettability of thesurface of the substrate is varied.

According to a preferred embodiment of the present invention, thephotocatalyst changes the wettability of light exposed areas throughoxidation, decomposition or the like of organic groups as a part of thebinder and additives to bring the exposed areas to a high criticalsurface tension state. This creates a large difference in wettabilitybetween the exposed areas and the unexposed areas to record patterninformation.

(Photocatalyst Material)

Preferred photocatalyst materials usable in the present inventioninclude, for example, metal oxides known as photosemiconductors, such astitanium oxide (TiO₂), zinc oxide (ZnO), tin oxide (SnO₂), strontiumtitanate (SrTiO₃), tungsten oxide (WO₃), bismuth oxide (Bi₂O₃), and ironoxide (Fe₂O₃). Among them, titanium oxide is particularly preferredbecause it has high band gap energy and is chemically stable, nontoxic,and easily available.

Titanium oxide as the photocatalyst may be in anatase form or rutileform with anatase form of titanium oxide being preferred. Specificexamples of anatase form of titanium oxide usable herein includehydrochloric acid peptization type titania sols (STS-02, average crystaldiameter 7 nm, manufactured by Ishihara Sangyo Kaisha Ltd.) and nitricacid peptization type titania sols (TA-15, average crystal diameter 12nm, manufactured by Nissan Chemical Industries Ltd.).

Preferably, the photocatalyst has a small particle diameter because thephotocatalytic reaction takes place efficiently to render the surfaceroughness of the photocatalyst-containing layer small. The averageparticle diameter is preferably not more than 50 nm, more preferably notmore than 20 nm.

The content of the photocatalyst in the photocatalyst-containing layeris preferably 5 to 60% by weight, more preferably 20 to 40% by weight.

(Binder Component)

According to a preferred embodiment of the present invention, the binderused in the photocatalyst-containing layer preferably has a bindingenergy high enough to avoid the decomposition of the main skeleton uponphotoexcitation of the photocatalyst, and example thereof include (1)organopolysiloxanes that hydrolyze and polycondensate a chloro- oralkoxysilane or the like by a sol-gel reaction or the like to developlarge strength and (2) organopolysiloxanes obtained by crosslinkingreactive silicones having excellent water repellency or oil repellency.

In the case of (1), the organopolysiloxane is composed mainly of ahydrolysis condensate or a cohydrolyzate of at least one member selectedfrom silicon compounds represented by general formula Y_(n)SiX_(4-n)wherein n is 1 to 3; Y represents an alkyl, fluoroalkyl, vinyl, amino,or epoxy group; and X represents a halogen or a methoxy, ethoxy, oracetyl group.

Specific examples thereof include methyltrichlorosilane,methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane,methyltriisopropoxysilane, methyl-tri-t-butoxysilane;ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane,ethyltriethoxysilane, ethyltriisopropoxysilane,ethyl-tri-t-butoxysilane; n-propyltrichlorosilane,n-propyltribromosilane, n-propyltrimethoxysilane,n-propyltriethoxysilane, n-propyltriisopropoxysilane,n-propyl-tri-t-butoxysilane; n-hexytrichlorosilane,n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane,n-hexyltriisopropoxysilane, n-hexyl-tri-t-butoxysilane;n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane,n-decyltriethoxysilane, n-decyltriisopropoxysilane,n-decyl-tri-t-butoxysilane; n-octadecyltrichlorosilane,n-octadecyltribromosilane, n-octadecyltriethoxysilane,n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane,n-octadecyl-tri-t-butoxysilane; phenyltrichlorosilane,phenylribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane,phenyltrisopropoxysilane, phenyl-tri-t-butoxysilane; tetrachlorosilane,tetrabromosilane, tetramethoxysilane, tetraethoxysilane,tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldichlorosilane,dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane;diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane,diphenyldiethoxysilane; phenylmethyldichlorosilane,phenylmethyldibromosilane, phenylmethyldimethoxysilane,phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane,trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxyhydrosilane,tri-t-butoxyhydrosilane; vinyltrichlorosilane, vinyltribromosilane,vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane,vinyl-tri-t-butoxysilane; trifluoropropyltrichlorosilane,trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane,trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane,trifluoropropyl-tri-t-butoxysilane; Yglycidoxypropylmethyldimethoxysilane, Yglycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane,γ-glycidoxypropyl-tri-t-butoxysilane;γ-methacryloxypropylmethyldimethoxysilane,γ-methacryloxypropylmethyldiethoxysilane,γ-methacryloxypropyltrimethoxysilane,γ-methacryloxypropyltriethoxysilane,γ-methacryloxypropyltriisopropoxysilane,γ-methacryloxypropyl-tri-t-butoxysilane;γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropyltriisopropoxysilane, γ-aminopropyl-tri-t-butoxysilane;γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane,γ-mercaptopropyl-tri-t-butoxysilane;β-(3,4-epoxycyclohexyl)ethyltirimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltriethoxysilane; and partial hydrolyzatesthereof; and mixtures thereof.

The binder is particularly preferably a polysiloxane containing afluoroalkyl group, specifically at least one member selected fromhydrolysis condensates and cohydrolysis condensates of the followingfluoroalkylsilanes. Polysiloxanes generally known as fluorosilanecoupling agents may also be used.

-   -   CF₃(CF₂)₃CH₂CH₂Si(OCH₃)₃,    -   CF₃(CF₂)₅CH₂CH₂Si(OCH₃)₃,    -   CF₃(CF₂)₇CH₂CH₂Si(OCH₃)₃,    -   CF₃(CF₂)₉CH₂CH₂Si(OCH₃)₃,    -   (CF₃)₂CF(CF₂)₄CH₂ CH₂Si(OCH₃)₃,    -   (CF₃)₂CF(CF₂)₆CH₂ CH₂Si(OCH₃)₃,    -   (CF₃)₂CF(CF₂)₈CH₂ CH₂Si(OCH₃)₃,    -   CF₃(C₆H₄)C₂H₄Si(OCH₃)₃,    -   CF₃(CF₂)₃(C₆H₄)C₂H₂Si(OCH₃)₃,    -   CF₃(CF₂)₅(C₆H₄)C₂H₄Si(OCH₃)₃,    -   CF₃(CF₂)₇(C₆H₄)C₂H₄Si(OCH₃)₃,    -   CF₃(CF₂)₃CH₂CH₂SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₅CH₂CH₂SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₇CH₂CH₂SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₉CH₂CH₂SiCH₃ (OCH₃)₂,    -   (CF₃)₂CF(CF₂)₄CH₂ CH₂SiCH₃ (OCH₃)₂,    -   (CF₃)₂CF(CF₂)₆CH₂ CH₂SiCH₃ (OCH₃)₂,    -   (CF₃)₂CF(CF₂)₈CH₂ CH₂SiCH₃ (OCH₃)₂,    -   CF₃(C₆H₄)C₂H₄SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₃(C₆H₄)C₂H₄SiCH₃(OCH₃)₂,    -   CF₃(CF₂)₅(C₆H₄)C₂H₄SiCH₃(OCH₃)₂,    -   CF₃(CF₂)₇(C₆H₄)C₂H₄SiCH₃(OCH₃)₂,    -   CF₃(CF₂)₃ CH₂ CH₂Si(OCH₂ CH₃)₃,    -   CF₃(CF₂)₅ CH₂ CH₂Si(OCH₂ CH₃)₃,    -   CF₃(CF₂)₇ CH₂ CH₂Si(OCH₂ CH₃)₃,    -   CF₃(CF₂)₉ CH₂ CH₂Si(OCH₂ CH₃)₃, and    -   CF₃(CF₂)₇SO₂N(C₂H₅)C₂H₄CH₂Si(OCH₃)₃.

Use of polysiloxanes containing fluoroalkyl groups as the binder resultsin markedly improved water repellency and oil repellency of thephotocatalyst-containing layer in its unexposed areas and can improvethe function of inhibiting deposition of lens compositions and coatingcompositions for black matrixes.

Examples of reactive silicones (2) include compounds having a skeletonrepresented by the following general formula.

—(Si(R¹)(R²)O)_(n)—

wherein n is an integer of two or more; and R¹ and R² represent asubstituted or unsubstituted allyl, alkenyl, aryl, or cyanoalkyl grouphaving 1 to 10 carbon atoms. Preferably, not more than 40% by mole ofthe whole is accounted for by vinyl, phenyl, or phenyl halide. R¹ and/orR² preferably represent a methyl group because the surface free energyof the silicone is the smallest. The molar proportion of the methylgroup is preferably not less than 60%. Further, the chain end or theside chain has in its molecular chain at least one reactive group, suchas a hydroxyl group.

A stable organosilicon compound not causing any crosslinking reaction,such as dimethylpolysiloxane, together with the organopolysiloxane, maybe incorporated into the binder.

(Other Components of Photocatalyst-Containing Layer)

A surfactant may be incorporated into the photocatalyst-containing layerpreferably used in the present invention from the viewpoint of loweringthe wettability of unexposed areas. The surfactant is not particularlylimited so far as it can be removed by decomposition. Specific examplesof preferred surfactants usable herein include hydrocarbon surfactants,such as NIKKOL BL, BC, BO, and BB series manufactured by NihonSurfactant Kogyo K.K.; and fluoro or silicone nonionic surfactants, suchas ZONYL FSN and FSO, manufactured by E.I. du Pont de Nemours & Co.,Surfluon S-141 and 145 manufactured by Asahi Glass Co., Ltd., MegafacF-141 and 144 manufactured by Dainippon Ink and Chemicals, Inc.,Ftergent F-200 and F-251, manufactured by Neos Co., Ltd.; Unidyne DS-401and 402 manufactured by Daikin Industries, Ltd., and Fluorad FC-170 and176 manufactured by Sumitomo 3M Ltd. Cationic, anionic and amphotericsurfactants may also be used.

Further, besides the surfactant, the following compound may beincorporated into the photocatalyst-containing layer preferably used inthe present invention: oligomers and polymers, such as polyvinylalcohol, unsaturated polyesters, acrylic resins, polyethylene, diallylphthalate, ethylene propylene diene monomer, epoxy resin, phenolicresin, polyurethane, melamine resin, polycarbonate, polyvinyl chloride,polyamide, polyimide, styrene butadiene rubber, chloroprene rubber,polypropylene, polybutylene, polystyrene, polyvinyl acetate, nylon,polyester, polybutadiene, polybenzimidazole, polyacrylonitrile,epichlorohydrin, polysulfide, and polyisoprene.

(Method for Forming Photocatalyst-Containing Layer)

The method for forming the photocatalyst-containing layer is notparticularly limited. For example, a photocatalyst-containing coatingliquid may be coated onto a substrate by spray coating, dip coating,roll coating, bead coating or the like to form aphotocatalyst-containing layer. When the coating liquid contains anultraviolet curable component as the binder, thephotocatalyst-containing composition layer may be formed on thesubstrate by curing through ultraviolet irradiation.

When a coating liquid containing a photocatalyst or the like is used,solvents used in the coating liquid is not particularly limited. Forexample, organic solvents, for example, alcohols, such as ethanol andisopropanol, may be used.

(Light for Exposure to Induce Photocatalytic Action)

The exposure light for inducing photocatalytic action is notparticularly limited so far as the photocatalyst can be excited.Examples thereof include ultraviolet light, visible light, infraredradiation and, in addition, electromagnetic waves and radiations havingshorter or longer wavelength than these lights.

For example, the anatase form of titania is used as the photocatalyst,the excitation wavelength thereof is not more than 380 nm. Therefore, inthis case, the photocatalyst can be excited by ultraviolet light.Ultraviolet light sources usable herein include mercury lamps, metalhalide lamps, xenon lamps, excimer laser, and other ultraviolet lightsources. The wettability of the layer surface may be varied by varyingthe intensity exposure and the like.

FIG. 25 is an explanatory view showing one embodiment of the process forproducing a microlens using the above photocatalyst according to apreferred embodiment of the present invention. As shown in FIG. 25 (A),a photocatalyst-containing layer 303 is formed on a substrate 301, aphotomask 304 is put on the photocatalyst-containing layer 303, andlight 305 is applied to the photocatalyst-containing layer 303 throughthe photomask 304 to form a modified photocatalyst-containing layer303′. Next, as shown in FIG. 25 (B), a composition for a lens ejectedthrough an ejection nozzle 306 and deposited onto the modifiedphotocatalyst-containing layer 303′ to form a lens 302.

Light Shielding Layer

The light shielding layer preferably used in the lens of the presentinvention is formed so that the position and the shape conform to theposition and the shape of the lens. The light shielding layer functionsto prevent incidence of unnecessary light around the lens into the lens.More preferably, the light shielding layer is provided on a microlensarray.

According to a preferred embodiment of the present invention, the lightshielding layer may be formed by any method without limitation.Preferably, however, as with the lens, the light shielding layer isformed by utilizing a difference in wettability. Specifically, a patternbased on a difference in wettability for a light shielding patterncorresponding to the lens pattern is formed on the backside of atransparent substrate that is the side on which the lens is not formed.A liquid containing a material for a light shielding layer is depositedonto areas having specific wettability for the light shielding layerpattern of the substrate, and the liquid containing a material for thelight shielding layer is cured to produce lenses having a lightshielding layer.

The material for the light shielding layer is not limited so far as itis generally used in the art. An example of the material for the lightshielding layer is a thin layer of a light shielding resin layer formedusing a coating material of an acrylic thermoplastic resin containingcarbon black.

FIG. 26 shows a cross-sectional view showing a microlens array having alight shielding layer according to a preferred embodiment of the presentinvention. In FIG. 26, a photocatalyst-containing layer 303 is providedon a substrate 301. A lens 302 is provided on thephotocatalyst-containing layer 303 in its areas other than the modifiedcatalyst-containing layer 303′. Further, the photocatalyst-containinglayer 303 is provided also on the substrate 301 in its side (backside)not provided with the lens 302, and a light shielding layer 307 isprovided on the modified photocatalyst-containing layer 303′.

FIG. 27 is a plan view of a microlens array having a light shieldinglayer as viewed from the side on which the light shielding layer isprovided. As can be seen from the drawing, an opening of the lightshielding layer 307 is provided at a position corresponding to thecenter of the lens 302.

Application to Image Pick-up Device

The microlens array according to a preferred embodiment of the presentinvention can be preferably used as a component adjacent to or inintimate contact with an image pick-up element, for example, CCD, inorder to enhance the photosensitivity of image pick-up devices. In thiscase, preferably, a light shielding layer is provided, for example, fromthe viewpoint of avoiding an adverse effect onto properties, such as alowering in contrast due to stray light. The thickness of thephotocatalyst-containing layer is preferably small for enhancement oflight transmission, prevention of the photocatalyst-containing layerfrom developing color due to interference of light, and other purposes.The thickness is preferably not more than 1 μm, more preferably not morethan 0.2 μm.

FIG. 28 is a cross-sectional view showing one embodiment of an imagepick-up device using a microlens array having a light shielding layer.In the image pick-up device, a microlens array 320 having a lightshielding layer 307 is provided on an image pick-up element section 318comprising a color filter 309 and a photoelectric transducer 301.Incident light 308 enters the image pick-up element section 318 throughthe microlens array.

The color microlens array according to a preferred embodiment of thepresent invention can have both the function of the color filter as aconstituent element of the image pick-up element and the function of themicrolens array. This can realize an image pick-up element that has asimple construction not using any color filter and the function of themicrolens array. In this case, preferably, a light shielding layer isprovided, for example, from the viewpoint of avoiding an adverse effecton properties, such as a lowering in contrast and a lowering in chromadue to stray light. The thickness of the photocatalyst-containing layeris preferably small for enhancement of light transmission, prevention ofthe photocatalyst-containing layer from developing color due tointerference of light, and other purposes. The thickness is preferablynot more than 1 μm, more preferably not more than 0.2 μm.

FIG. 29 is a cross-sectional view showing one embodiment of an imagepick-up device using a microlens array 321 having a light shieldinglayer 307. In the image pick-up device, a color microlens having a lightshielding layer is provided on a photoelectric transducer. Incidentlight 308 enters the photoelectric transducer 310 through the colormicrolens array.

Application to Display

The microlens array according to a preferred embodiment of the presentinvention may be preferably used, for example, as a component adjacentto or in intimate contact with displays, for example, liquid crystaldisplays, in order to enhance the brightness in the direction of aviewer. In this case, preferably, a light shielding layer is provided inorder to inhibit an adverse effect of external light around displays,such as indoor lighting and sunlight, and to improve display quality.Further, the thickness of the photocatalyst-containing layer ispreferably small for enhancement of light transmission, prevention ofthe photocatalyst-containing layer from developing color due tointerference of light, and other purposes. The thickness is preferablynot more than 1 μm, more preferably not more than 0.2 μm.

FIG. 30 is a cross-sectional view showing one embodiment of a liquidcrystal display using a microlens array 320 having a light shieldinglayer 307. A microlens provided with a light shielding layer is providedon a liquid crystal display. Light emitted from the liquid crystaldisplay is released into the exterior as luminescence 311 through themicrolens array.

The color microlens array according to a preferred embodiment of thepresent invention can have both the function of a color filter as aconstituent element of the display and the function of the microlensarray. This can realize a display that has a simple construction notusing any color filter and the function of the microlens array.

In this case, preferably, a light shielding layer is provided in orderto inhibit an adverse effect of external light around displays, such asindoor lighting and sunlight, and to improve display quality. Further,the thickness of the photocatalyst-containing layer is preferably smallfor enhancement of light transmission, prevention of thephotocatalyst-containing layer from developing color due to interferenceof light, and other purposes. The thickness is preferably not more than1 μm, more preferably not more than 0.2 μm.

FIG. 31 is a cross-sectional view showing one embodiment of a liquidcrystal display using a color microlens array having a light shieldinglayer. The liquid crystal display comprises a light source 314, a liquidcrystal element 313, and a color microlens array 321 having a lightshielding layer 307. Light emitted through the liquid crystal element313 from the light source 314 is released into the exterior asluminescence 311 through the color microlens array 321.

Re: Fourth Invention D

According to the present invention, patterns, such as designs, images,and letters, are formed on an original plate for lithography having aphotocatalyst-containing layer that can cause a chemical change inmaterials around the photocatalyst upon light irradiation, and theresultant plate is used as a lithographic plate.

The mechanism of action of the photocatalyst typified by titanium oxideaccording to the present invention has not been fully elucidated.However, it is considered that carriers produced by light irradiationchanges the chemical structure of the organic material through a directreaction with a neighboring compound, or otherwise by active oxygenspecies produced in the presence of oxygen and water.

Proposals utilizing the photocatalytic action include one wherein oilstains are decomposed by light irradiation to hydrophilify the oilstains, enabling the oil stains to be washed away by water, one whereina high critical surface tension film is formed on the surface of glassor the like to impart antifogging properties, and one wherein aphotocatalyst-containing layer is formed on the surface of tiles or thelike to form the so-called antimicrobial tiles or the like that canreduce the number of bacteria floating in air.

According to the present invention, a change in wettability betweenareas where a pattern is formed and areas where no pattern is formed iscreated through the action of decomposition of organic materials by thephotocatalyst, thereby enhancing the receptivity of the pattern-formedareas to printing ink or the ink repellency to obtain a lithographicplate.

Photocatalysts usable in the lithographic plate according to the presentinvention include metal oxides known as photosemiconductors, such astitanium oxide (TiO₂), zinc oxide (ZnO), tin oxide (SnO₂), strontiumtitanate (SrTiO₃), tungsten oxide (WO₃), bismuth oxide (Bi₂O₃), and ironoxide (Fe₂O₃). Among them, titanium oxide is particularly preferredbecause it has high band gap energy and is chemically stable, nontoxic,and easily available.

Titanium oxide may in anatase form or rutile form with anatase form oftitanium oxide being preferred.

Preferably, the anatase form of titanium oxide has an average particlediameter of not more than 20 nm. Examples of anatase form of titaniumoxide usable herein include hydrochloric acid peptization type titaniasols (STS-02, average crystal diameter 7 nm, manufactured by IshiharaSangyo Kaisha Ltd.) and nitric acid peptization type titania sols(TA-15, average crystal diameter 12 nm, manufactured by Nissan ChemicalIndustries Ltd.).

The photocatalyst-containing layer according to the present inventionmay be formed by dispersing a photocatalyst in a binder. Thephotocatalyst has a fear of decomposing the binder as well uponphotoexcitation. Therefore, the binder should be composed mainly of amaterial having high binding energy. When use as a printing plate istaken into consideration, plate wear and abrasion resistance are alsorequired of the photocatalyst-containing layer. Therefore, the binder ispreferably a silicone resin that has a main skeleton having high bindingenergy, is crosslinked by a sol-gel reaction or the like to developlarge strength, and, through photocatalytic action, undergoes a changein wettability. The silicone resin is composed mainly of a hydrolysiscondensate or a cohydrolysis condensate of at least one member selectedfrom silicon compounds represented by general formula Y_(n)SiX_(4-n),wherein n is 1 to 3; Y represents an alkyl, fluoroalkyl, vinyl, amino,or epoxy group; and X represents a halogen or a methoxy, ethoxy, oracetyl group.

Specific examples thereof include methyltrichlorosilane,methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane,methyltriisopropoxysilane, methyl-tri-t-butoxysilane;ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane,ethyltriethoxysilane, ethyltniisopropoxysilane,ethyl-tri-t-butoxysilane; n-propyltrichlorosilane,n-propyltribromosilane, n-propyltrimethoxysilane,n-propyltriethoxysilane, n-propyltriisopropoxysilane,n-propyl-tri-t-butoxysilane; n-hexytrichlorosilane,n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltrimethoxysilane,n-hexylhtisopropoxysilane, n-hexyl-tri-t-butoxysilane;n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane,n-decyltrimethoxysilane, n-decyltriisopropoxysilane,n-decyl-tri-t-butoxysilane; n-octadecyltrichlorosilane,n-octadecyltribromosilane, n-octadecyltrimethoxysilane,n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane,n-octadecyl-tri-t-butoxysilane; phenyltrichlorosilane,phenylribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane,phenyltriisopropoxysilane, phenyl-tri-t-butoxysilane; tetrachlorosilane,tetrabromosilane, tetramethoxysilane, tetraethoxysilane,tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldichlorosilane,dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane;diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane,diphenyldiethoxysilane; phenylmethyldichlorosilane,phenylmethyldibromosilane, phenylmethyldimethoxysilane,phenylmethyldiethoxysilane; trichlorohydiosilane, tribromohydrosilane,trimethoxyhydrosilane, haiethoxyhydrosilane, triisopropoxyhydrosilane,tri-t-butoxyhydrosilane; vinyltrichlorosilane, vinylthibromosilane,vinyl-tri-t-butoxysilane, vinyltriethoxysilane,vinyltriisopropoxysilane, vinyl-tri-t-butoxysilane;trifluoropropyltrichlorosilane, tlifluoropropyltTibromosilane,trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane,trifluoropropyltriisopropoxysilane, trifluoropropyl-tri-t-butoxysilane;γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxpropyltimetloxysilane,γ-glycidoxypropyltietlhoxysilane, γ-glycidoxypropyltriisopropoxysilane,γ-glycidoxypropyl-tri-t-butoxysilane;γ-methacryloxypropylmethyldimethoxysilane,γ-methacryloxypropylmethyldiethoxysilane,γ-methacryloxypropyltrimethoxysilane,γ-methacryloxypropyltriethoxysilane,γ-methacryloxypropyltriisopropoxysilane,γ-methacryloxypropyl-tri-t-butoxysilane;γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropyltiisopropoxysilane, γ-aminopropyl-tri-t-butoxysilane;γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane,7-mercaptopropyl-tri-t-butoxysilane;β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltriethoxysilane; and partial hydrolyzatesthereof; and mixtures thereof.

The photocatalyst-containing layer in the original plate for lithographyaccording to the present invention may contain a fluoroalkyl chain,specifically at least one member selected from hydrolysis condensatesand cohydrolysis condensates of the following fluoroalkylsilanes.Further, compounds having fluoroalkyl groups include the followingcompounds. Compounds generally known as fluorosilane coupling agents mayalso be used.

-   -   CF₃(CF₂)₃CH₂CH₂Si(OCH₃)₃,    -   CF₃(CF₂)₅CH₂CH₂Si(OCH₃)₃,    -   CF₃(CF₂)₇CH₂CH₂Si(OCH₃)₃,    -   CF₃(CF₂)₉CH₂CH₂Si(OCH₃)₃,    -   (CF₃)₂CF(CF₂)₄CH₂ CH₂Si(OCH₃)₃,    -   (CF₃)₂CF(CF₂)₆CH₂ CH₂Si(OCH₃)₃,    -   (CF₃)₂CF(CF₂)₈CH₂ CH₂Si(OCH₃)₃,    -   CF₃(C₆H₄)C₂H₄Si(OCH₃)₃,    -   CF₃(CF₂)₃(C₆H₄)C₂H₁Si(OCH₃)₃,    -   CF₃(CF₂)₅(C₆H₄)C₂H₄Si(OCH₃)₃,    -   CF₃(CF₂)₇(C₆H₄)C₂H₄Si(OCH₃)₃,    -   CF₃(CF₂)₃CH₂CH₂SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₅CH₂CH₂SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₇CH₂CH₂SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₉CH₂CH₂SiCH₃ (OCH₃)₂,    -   (CF₃)₂CF(CF₂)₄CH₂ CH₂SiCH₃ (OCH₃)₂,    -   (CF₃)₂CF(CF₂)₆CH₂ CH₂SiCH₃ (OCH₃)₂,    -   (CF₃)₂CF(CF₂)₈CH₂ CH₂SiCH₃ (OCH₃)₂,    -   CF₃(C₆H₄)C₂H₄SiCH₃ (OCH₃)₂,    -   CF₃(CF₂)₃(C₆H₄)C₂H₄SiCH₃(OCH₃)₂,    -   CF₃(CF₂)₅(C₆H₄)C₂H₄SiCH₃(OCH₃)₂,    -   CF₃(CF₂)₇(C₆H₄)C₂H₄SiCH₃(OCH₃)₂,    -   CF₃(CF₂)₃ CH₂ CH₂Si(OCH₂ CH₃)₃,    -   CF₃(CF₂)₅ CH₂ CH₂Si(OCH₂ CH₃)₃,    -   CF₃(CF₂)₇ CH₂ CH₂Si(OCH₂ CH₃)₃,    -   CF₃(CF₂)₉ CH₂ CH₂Si(OCH₂ CH₃)₃,

Further, titanium, aluminum, zirconium, and chromium coupling agents mayalso be used.

Use of these coupling agents can enhance crosslinking and increase thestrength.

Use of these fluoroalkylsilanes can markedly improve the oil repellencyand can develop the function of inhibiting the deposition of the resincomposition.

The content of the photocatalyst in the layer containing thephotocatalyst and the organosiloxane is preferably 5 to 50% by weight,more preferably 20 to 40% by weight. The photocatalyst and the binderare dispersed in a solvent to prepare a coating liquid following bycoating. Solvents usable herein include alcoholic organic solvents, suchas ethanol and isopropanol.

Preferably, the photocatalyst has a small particle diameter because thephotocatalytic reaction takes place efficiently. The average particlediameter is preferably not more than 50 nm, more preferably not morethan 20 nm.

The excitation wavelength of the anatase form of titania is not morethan 380 nm. Therefore, the excitation of this type of catalysts shouldbe carried out using ultraviolet light. Ultraviolet light sources usableherein include mercury lamps, metal halide lamps, xenon lamps, excimerlamps, excimer layer, YAG laser, and other ultraviolet light sources.The wettability of the film surface may be varied by varying theultraviolet light intensity, exposure and the like.

When the exposure is carried out using a fine beam of a laser or thelike, a desired image pattern may be directly formed without use of anymask. In the case of other light sources, a pattern is formed by lightirradiation using a mask with a desired pattern formed thereon. Patternforming masks usable herein include masks wherein a pattern is formed ona metal sheet, such as vapor deposition masks, photomasks wherein apattern is formed using a metallic chromium on a glass sheet, and, forprinting applications, plate preparation films.

When a mask is used, the resolution can be enhanced by conducting theexposure in intimate contact of the mask with thephotocatalyst-containing layer. In this case, however, the sensitivityis remarkably lowered. Preferably, the exposure is carried out whileleaving a spacing of about 100 μm between the mask and thephotocatalyst-containing layer.

The photocatalyst-containing layer may be rendered sensitive to visiblelight and the like by ion doping, by addition of fluorescent materials,or addition of photosensitive dyes. Examples of photosensitive dyeswhich may be added to the structure for pattern formation includecyanine dyes, carbocyanine dyes, dicarbocyanine dyes, hemicyanine dyes,and other cyanine dyes. Other useful dyes include diphenylmethane dyes,for example, triphenylmethane dyes, such as Crystal Violet and basicfuchsine, xanthene dyes, such as Rhodamine B, Victoria Blue, BrilliantGreen, Malachite Green, Methylene Blue, pyrylium salts, benzopyryliumsalts, trimethinebenzopyrylium salts, and triallylcarbonium salts.

The photocatalyst-containing coating liquid may be coated onto thesubstrate by spray coating, dip coating, roll coating, bead coating orthe like. When an ultraviolet curable component is contained as thebinder, curing by ultraviolet irradiation results in the formation of aphotocatalyst-containing composition layer on the substrate. Substratesusable in the lithographic plate according to the present inventioninclude glasses, metals, plastics, woven fabrics, and nonwoven fabrics.

The present invention will be described with reference to theaccompanying drawings. FIGS. 32 and 33 are diagrams showing oneembodiment of the process for producing a printing plate according tothe present invention.

As shown in FIG. 32 (A), an original plate 401 for a printing plate maybe produced by forming a photocatalyst-containing composition layer 441directly or through a primer layer 403 on a substrate 402. As shown inFIG. 32 (B), in order to record pattern information, exposure 406 iscarried out in a predetermined pattern 405. As shown in FIG. 32 (C),alkyl chains of the silicone compound are converted to OH groups throughthe action of a photocatalyst 407 to change the wettability of thesurface according to the exposed pattern. Unexposed areas are in thestate of low surface free energy 408, while exposed areas undergo achange in wettability. Therefore, coating of a resin layer composition409 permits a layer of the resin layer composition 409 to be selectivelyformed on the wettability-varied areas 410.

Next, as shown in FIG. 33 (A), heat or ultraviolet light is applied tocure the resin layer composition 409, thereby forming a resin layer 411that can withstand printing and the like. Further, as shown in FIG. 33(B), after the formation of the resin layer, the whole area exposure 412is carried out without a mask and the like.

As shown in FIG. 33 (C), upon exposure, the action of the photocatalyst407 in areas not provided with the cured layer permits the alkyl chainof the silicone compound to be converted to OH group and the low surfacefree energy areas 408 to be brought to high surface free energy areas413.

The lithographic plate thus obtained may be used in any of waterlessplating and plating using dampening water.

FIG. 34 is a diagram illustrating use of a lithographic plate inprinting.

FIG. 34 (A) shows an embodiment wherein the lithographic plate is usedas a waterless plate in printing, and FIG. 34 (B) shows an embodimentwherein the lithographic plate is used as a printing plate usingdampening water.

When the resin layer 411 having low surface free energy is inkrepellent, as shown in FIG. 34 (A), the resin layer 411, due to the inkrepellency, repels ink 414 and cannot receive the ink. The ink isdeposited only onto areas not provided with the resin layer, andprinting is performed by transfer of the deposited ink onto a printingmedium.

On the other hand, when the resin layer 411 is receptive to ink,dampening water 415 is deposited onto areas other than the resin layer411. Since the resin layer 411 can receive ink, printing can be carriedout by transfer of ink onto a printing medium.

Further, incorporation of a photochromic material, which undergoes achange in color upon light irradiation, such as spiropyran, an organicdye decomposable through photocatalytic action or the like into thecomposition can form a visualized pattern.

An embodiment will be described wherein the original plate for aprinting plate is a waterless plate.

The ink repellent layer used in the present invention may be formed of asilicone rubber or a fluorocompound, such as a rubber having in itsmolecule fluorine with the silicone rubber being preferred. The siliconerubber layer is obtained by sparsely crosslinking a linearorganopolysiloxane, preferably dimethylpolysiloxane. A typical siliconerubber layer is formed of a silicone rubber comprising repeating unitsrepresented by the following formula D-1:

wherein n is an integer of two or more; and R¹ and R² each independentlyrepresent a substituted or unsubstituted alkyl, alkenyl, aryl, orcyanoalkyl group having 1 to 10 carbon atoms. Not more than 40% of thewhole R¹ and R² is accounted for by vinyl, phenyl, vinyl halide orphenyl halide. Not less than 60% of R¹ and R² is preferably accountedfor by a methyl group. Further, the chain end or the side chain has inits molecular chain at least one hydroxyl group.

When the silicone rubber later applied to the printing plate accordingto the present invention may be a condensation tripe crosslinkablesilicone rubber (an RTV or LTV silicone rubber). A silicone rubber witha part of R¹ and R² of the organopolysiloxane chain being substituted bya hydrogen atom may also be used as the silicone rubber. Further,silicone rubbers may also be used wherein ends represented by formulaeD-2, D-3, and D-4 are crosslinked. In some cases, an excessive amount ofa crosslinking agent is allowed to exist.

wherein R¹ and R² are as defined in formula D-1; and R³ and R⁴ representa monovalent lower alkyl. A catalyst, such as a carboxylate of a metal,such as till, zinc, lead, calcium, or manganese, for example, dibutyltinlaurate, tin(II) octate, or a napthtenate of the above metal, orchloroplatinic acid, is added to the silicone rubber which is subjectedto condensation tape crosslinking.

Regarding the formulation of the components used in the condensationtype silicone rubber, for example, to 100 parts by weight of thecompound comprising repeating units represented by formula D-1 are added0.1 to 100 parts by weight of the compound having a structurerepresented by formula D-3 or D-4 and optionally 0 to 50 parts by weightof a conventional catalyst.

Further, a silicone rubber layer wherein crosslinking has been carriedout by an addition reaction of formula D-5 with formula D-6. Thesilicone rubber is produced by reacting a polyvalenthydrodieneorganopolysiloxane with a polysiloxane having in its moleculetwo or more bonds of formula D-6, preferably by crosslinking curing of acomposition comprising the following components:

Specifically,

(1) Organopolysiloxane having at least 100 parts by weight two alkenylgroups (preferably vinyl group), per molecule, directly bonded tosilicon atom (2) Organohydrogenpolysiloxane 0.1 to 1000 parts by weighthaving at least two groups of formula 5 per molecule (3) Additioncatalyst 0.00001 to 10 parts by weight

The alkenyl group in the component (1) may be located at the end or atan intermediate position of the molecular chain. Organic groups otherthan the alkenyl group are substituted or unsubstituted alkyl group andaryl group. The component (1) may have a very small amount of hydroxylgroup.

Hydrogen in the component (2) may be located at the end or at anintermediate position of the molecular chain. Organic groups other thanhydrogen are selected from the same group as described in connectionwith the component (1). Regarding the organic group in the components(1) and (2), not less than 60% of the total number of groups ispreferably accounted for by a methyl group from the viewpoint of inkrepellency.

For the components (1) and (2), the molecular structure may be ofstraight chain, cyclic, or branched chain. Preferably, the molecularweight of any one of the components (1) and (2) exceeds 1000 from theviewpoint of properties of rubber. Further, preferably, the molecularweight of the component (2) exceeds 1000.

Examples of the component (1) include α, ω-divinylpolydimethylsiloxaneand a methylvinyl siloxane/dimethylsiloxane copolymer with both endsthereof being a methyl group.

Examples of the component (2) includes polydimethylsiloxane with bothends thereof being a hydrogen atom, α,ω-dimethylpolymethylhydrodienesiloxane, amethylhydrodienesiloxane/dimethylsiloxane copolymer with both endsthereof being a methyl group, and a cyclic polymethylhydrodienesiloxane.

The addition catalyst in the component (3) may be properly selected fromconventional catalysts. Platinum compounds are particularly preferred.Examples thereof include platinum, platinum chloride, chloroplatinicacid, and olefin coordinated platinum.

Vinyl-containing organopolysiloxanes, such astetracyclo(methylvinyl)siloxane, carbon-carbon triple bond-containingalcohols, acetone, methyl ethyl ketone, methanol, ethanol, propyleneglycol monomethyl ether and other crosslinking inhibitors may be addedfrom the viewpoint of regulating the curing rate of the composition. Inthese compositions, upon mixing of the three components, an additionreaction occurs to initiate curing. The curing rate rapidly increaseswith increasing the reaction temperature. For this reason, in order toelongate the pot life for the composition to be converted to rubber and,at the same time, to shorten the curing time on thephotocatalyst-containing layer, curing conditions are preferably suchthat, until the composition is completely cured, the composition is heldat such high temperature conditions that the properties of the substrateand the photocatalyst-containing layer remains unchanged. This ispreferred from the viewpoint of stable adhesion to thephotocatalyst-containing layer.

In addition to the above components, conventional adhesion impartingagents, such as alkenyltnialloxysilanes, hydroxy-containingorganopolysiloxanes as the composition of the condensation type siliconerubber layer, and silane (or siloxane) containing hydrolyzable functiongroups may be added to these compositions. Further, conventionalfillers, such as silica, may also be added from the viewpoint ofimproving the strength of the rubber.

Further, instead of the silicone rubber, a fluororesin may be used asthe ink repellent layer. Fluororesins usable herein are as follows.

(1) Copolymer resin of perfluoroalkyl methacrylate and acrylic monomerhaving hydroxy group, e.g., 2-hydroxyethyl methacrylate

(2) Copolymer resin of perfluoroalkyl methacrylate and glycidylmethacrylate

(3) Copolymer resin of perfluoroalkyl methacrylate and methacrylic acid

(4) Copolymer resin of perfluoroalkyl methacrylate and maleic anhydride

When the fluororesin has both an active hydrogen functional group and afunctional group reactive with active hydrogen, or when a mixture of afluororesin having an active hydrogen functional group with afluororesin having a functional group reactive with active hydrogen isused, a crosslinking agent may be used.

Regarding the proportions of the components in the fluororesin layer,preferably 60 to 100% by weight, more preferably 80 to 98% by weight, ofthe whole layer is accounted for by fluororesin.

Next, the plate used with dampening water will be described.

In the plate used with dampening water, materials for the resin layer inwhich ink receptive areas are formed include, for example, acrylicresins using methacrylic acid, methacrylic esters or the like, vinylacetate resin, copolymer of vinyl acetate with ethylene or vinylchloride or the like, vinyl chloride resin, vinylidene chloride resin,vinyl acetal resin, such as polyvinylbutyral, polystyrene, copolymersincluding styrene/butadiene copolymer and styrene/methacrylic estercopolymer, polyethylene, polypropylene and chlorination productsthereof, polyester resins (for example, polyethylene terephthalate,polyethylene isophthalate, and polycarbonate of bisphenol A), polyamideresins (for example, polycapramide, polyhexamethylene adipamide, andpolyhexamethylene sebacamide), phenolic resin, xylene resin, alkydresin, vinyl-modified alkyd resin, gelatin, cellulose ester derivatives,such as carboxymethylcellulose, waxes, polyolefins, and waxes. The resincomposition is coated, and the coating is cured by heat or light. Thus,patterned areas having good ink receptivity and plate wear are formed.

Coating methods usable herein include roll coating, air knife coating,bar coating, and spin coating.

Further, according to the present invention, coating to form a thickfilm can prevent light to reach the underlying layer. This can preventthe photocatalytic reaction.

EXAMPLES

The following examples further illustrate the present invention.

Example A-1

30 g of GlascaHPC7002 (Japan Synthetic Rubber Co., Ltd.) and 10 g ofGlasca HPC402H (Japan Synthetic Rubber Co., Ltd.), an alkylalkoxysilane,were mixed together. The mixture was stirred for 5 min in a stirringapparatus. The resultant solution was spin coated on a glass substratehaving an area of 7.5 cm². The coated substrate was dried at atemperature of 150° C. for 10 min. Thus, a 2 μm-thick sodium ion blocklayer was formed.

Next, 15 g of Glasca HPC7002 (Japan Synthetic Rubber Co., Ltd.), 5 g ofGlasca HPC402H Japan Synthetic Rubber Co., Ltd.), and a titania sol(TA-15, manufactured by Nissan Chemical Industries Ltd.) were mixedtogether. The resultant solution was spin coated onto the substrate witha sodium ion block layer formed thereon. The assembly was dried at atemperature of 150° C. for 10 min, permitting hydrolysis andpolycondensation to proceed. Thus, a structure for pattern formationcomprising a 3 μm-thick photocatalyst-containing layer with aphotocatalyst being strongly fixed through an organopolysiloxane wasprepared.

The structure for pattern formation was irradiated with ultravioletlight at an intensity of 6.6 mW/cm² using a xenon lamp. In this case, achange in contact angle between the structure and water with the elapseof time was measured with a contact angle goniometer (Model CA-Z,manufactured by Kyowa Interface Science Co., Ltd.). The results areshovel in FIG. 5. As is apparent from the drawing, the contact anglegradually decreased and reached not more than 10°.

Separately, the structure for pattern formation was irradiated withultraviolet light through a lattice-like mask. Exposure to ultravioletlight at an intensity of 6.6 mW/cm² for 6 hr using a xenon lamp resultedin the formation of a pattern wherein the wettability of exposed areasand the wettability of unexposed areas were different from each otherand were 90 and 102°, respectively.

Example A-2

A 20 wt % dimethylformamide solution of a composition for a primer layer(Kan-coat 90T-25-3094, manufactured by Kansai Paint Co., Ltd.) wascoated on a 0.15 mm-thick degreased aluminum sheet. The coated aluminumsheet was dried at 200° C. for 1 min. Thus, a 3 μm-thick primer layerwas formed. A photocatalyst-containing layer as described in Example A-1was formed on the primer layer to prepare an original plate for awaterless printing plate.

Subsequently, a pattern was formed under conditions of Nd:YAG laser (355nm A-Physic Star Line) and recording energy 300 mJ/cm². The printingplate thus obtained was mounted on an offset printing machine (Alpha NewAce, manufactured by Alpha Giken K. K.), and printing was carried out ona coated paper using an ink for waterless printing (Inctec Waterless SDeep Blue, manufactured by The Inctec Inc.) at a printing speed of 5000sheets/hr. As a result, 20,000 sheets of good prints could be obtained.

Printing was carried out in the same manner as described above, exceptthat exposure was carried out using, instead of the laser, a xenon lampthrough a gradation negative film having halftone dots of 2 to 98% with175 lines/in. As a result, good prints could be obtained.

Example A-3

3 g of Glasca HPC7002 (Japan Synthetic Rubber Co., Ltd.), a silica sol,and 1 g of HPC402H (Japan Synthetic Rubber Co., Ltd.), analkylalkoxysilane, were mixed together. The mixture was stirred for 5min. The resultant solution was spin coated on a glass substrate havingan area of 7.5 cm². Thus, a 2 μm-thick sodium ion block layer wasformed.

Next, 3 g of isopropyl alcohol, 0.75 g of a silica sol (Glasca HPC7002,manufactured by Japan Synthetic Rubber Co., Ltd.), 0.25 g of analkylalkoxysilane (Glasca HPC402H, manufactured by Japan SyntheticRubber Co., Ltd.), and 0.15 g of a fluoroalkylsilane (MF-160Emanufactured by Tohchem Products Corporation: a 50 wt % isopropyl ethersolution ofN-[3-(trimethoxysilyl)propyl]-N-ethylperfluorooctanesulfonamide) weremixed together. The resultant dispersion was stirred for 20 min whilemaintaining the temperature at 100° C. Thereafter, 2 g of titanium oxide(titanium oxide coating liquid ST-K01, solid content 10% by weight,manufactured by Ishihara Sangyo Kaisha Ltd.) was added thereto, followedby stirring for additional 30 min.

The resultant dispersion was spin coated on the substrate with a sodiumblock layer formed thereon. The assembly was dried at a temperature of150° C. for 10 min, permitting hydrolysis and polycondensation toproceed. Thus, a 3 μm-thick photocatalyst-containing layer with aphotocatalyst being strongly fixed through an organopolysiloxane wasformed. The average roughness of the surface of thephotocatalyst-containing layer was measured by the tracer method andfound to be Ra=2 nm.

Further, the photocatalyst-containing layer was irradiated withultraviolet light at an intensity of 70 mW/cm² for 2 min using a highpressure mercury lamp through a lattice-like mask. In this case, thecontact angle of the photocatalyst-containing layer with water andn-octane was measured with a contact angle goniometer (Model CA-Z,manufactured by Kyowa Interface Science Co., Ltd.). The results areshown in Table A-4.

Example A-4

A sodium ion block layer was prepared in the same manner as in ExampleA-3. Next, 3 g of isopropyl alcohol, 0.4 g of an organosilane (TSL8113,manufactured by Toshiba Silicone Co., Ltd.), 0.15 g of afluoroalkylsilane (MF-160E, manufactured by Tohchem ProductsCorporation: a 50 wt % isopropyl ether solution ofN-[3-(trimethoxysilyl)propyl]-N-ethylperfluorooctanesulfonamide), and 2g of titanium oxide (titanium oxide coating liquid ST-K01, solid content10% by weight, manufactured by Ishihara Sangyo Kaisha Ltd.) were mixedtogether. The resultant dispersion was stirred for 20 min whilemaintaining the temperature at 100° C. The resultant dispersion was spincoated on the substrate with a sodium block layer formed thereon. Theassembly was dried at a temperature of 150° C. for 10 min, permittinghydrolysis and polycondensation to proceed. Thus, a 3 μm-thickphotocatalyst-containing layer with a photocatalyst being strongly fixedin an organopolysiloxane was formed. The average roughness of thesurface of the photocatalyst-containing layer was measured by the tracermethod and found to be Ra=2 nm. Further, the photocatalyst-containinglayer was irradiated with ultraviolet light at an intensity of 70 mW/cm²for 2 min using a high pressure mercury lamp through a lattice-likemask. In this case, the contact angle of the photocatalyst-containinglayer with water and n-octane was measured with a contact anglegoniometer (Model CA-Z, manufactured by Kyowa Interface Science Co.,Ltd.). The results are shown in Table A-4.

Example A-5

A 0.3 μm-thick photocatalyst-containing layer was spin coated onto apolycarbonate substrate in the same manner as in Example A-4. Thephotocatalyst-containing layer was irradiated with ultraviolet light atan intensity of 70 mW/cm² for 2 min using a high pressure mercury lampthrough a chart mask with a resolution of 50 lp/mm.

Various liquids having known surface tension were dropped on thephotocatalyst-containing layer to measure the contact angle between thephotocatalyst-containing layer and the liquids with a contact anglegoniometer (Model CA-Z, manufactured by Kyowa Interface Science Co.,Ltd.), and the critical surface tension was determined by Zismanplotting. As a result, the critical surface tension was 14.6 mN/m forunexposed areas and was 72.3 mN/m for exposed areas.

Next, an ink for waterless lithography (Inctec Waterless S Deep Blue,manufactured by The Inctec Inc.) was coated on the whole area of theexposed photocatalyst-containing layer by means of an RI tester (ModelRI-2 tester, manufactured by Ishlawajima Industrial Machinery Co.,Ltd.). As shown in FIG. 6, in the unexposed areas, the oil repellentnature repelled the ink, and the ink was selectively coated only in theexposed areas. Thus, a deep blue stripe pattern 118 of 50 lp/mm wasobtained on a transparent polycarbonate substrate 102 through aphotocatalyst layer 104.

Example A-6

3 g of Glasca HPC7002 (Japan Synthetic Rubber Co., Ltd.), a silica sol,and 1 g of HPC402H (Japan Synthetic Rubber Co., Ltd.), analkylalkoxysilane, were mixed together. The mixture was stirred for 5min. The resultant solution was spin coated on a 0.15 mm-thick degreasedaluminum sheet to form a 2 μm-thick primer layer.

Next, photocatalyst-containing layers as described in Examples A-3 andA-4 were formed on the primer layer to obtain original plates forwaterless printing plates.

Subsequently, a pattern was formed under conditions of Nd:YAG laser (355nm A-Physic Star Line) and recording energy 200 mJ/cm². The printingplates thus obtained were mounted on an offset printing machine (AlphaNew Ace, manufactured by Alpha Giken K.K.), and printing was carried outon a coated paper using an ink for waterless printing (Inctec WaterlessS Deep Blue, manufactured by The Inctec Inc.) at a printing speed of5000 sheets/hr. As a result, 20,000 sheets of good prints could beobtained.

Further, printing properties were evaluated in the same manner asdescribed above, except that exposure was carried out using, instead ofthe laser, a high pressure mercury lamp at an intensity of 70 mW/cm² for2 min through a gradation negative pattern having halftone dots of 2 to98% with 175 lines/in. As a result, good prints could be obtained.

Example A-7

A sodium ion block layer was prepared in the same manner as in ExampleA-3. Next, 3 g of isopropyl alcohol, 2.2 g of an organosilane (TSL8113,manufactured by Toshiba Silicone Co., Ltd.), 0.15 g of afluoroalkylsilane (MF-160E, manufactured by Tohchem ProductsCorporation: a 50 wt % isopropyl ether solution ofN-[3-(trimethoxysilyl)propyl]-N-ethylperfluorooctanesulfonamide), and0.2 g of titanium oxide powder (ST-21, average particle diameter 20 nm,manufactured by Ishihara Sangyo Kaisha Ltd.) were mixed together. Theresultant dispersion was stirred for 20 min while maintaining thetemperature at 100° C. The resultant dispersion was spin coated on thesubstrate with a sodium ion block layer formed thereon. The assembly wasdried at a temperature of 150° C. for 10 min, permitting hydrolysis andpolycondensation to proceed. Thus, a 3 μm-thick photocatalyst-containinglayer with a photocatalyst being strongly fixed in an organosiloxane wasformed. The average roughness of the surface of thephotocatalyst-containing layer was measured by the tracer method andfound to be Ra=4 nm. Further, the photocatalyst-containing layer wasirradiated with ultraviolet light at an intensity of 70 mW/cm² for 5 minusing a high pressure mercury lamp through a lattice-like mask. In thiscase, the contact angle of the photocatalyst-containing layer with waterand n-octane was measured with a contact angle goniometer (Model CA-Z,manufactured by Kyowa Interface Science Co., Ltd.). The results areshown in Table A-4.

Example A-8

A 0.3 μm-thick photocatalyst-containing layer formed in the same manneras in Example A-7 was irradiated with ultraviolet light at an intensityof 70 mW/cm² for 5 min using a high pressure mercury lamp through a maskwith light shielding layers having a size of 150×300 μm disposed atintervals of 30 μm.

Various liquids having known surface tension were dropped on thephotocatalyst-containing layer to measure the contact angle between thephotocatalyst-containing layer and the liquids with a contact anglegoniometer (Model CA-Z, manufactured by Kyowa Interface Science Co.,Ltd.), and the critical surface tension was determined by Zismanplotting. As a result, the critical surface tension was 15.4 mN/m forunexposed areas and was 73.3 mN/m for exposed areas.

Next, 4 g of carbon black (#950, manufactured by Mitsubishi ChemicalCorporation), 0.7 g of polyvinyl alcohol (Gosenol AH-26, manufactured byNippon Synthetic Chemical Industry Co., Ltd.), and 95.3 g of water weremixed together and dissolved with heating. The solution was centrifugedat 12000 rpm and filtered through a 1-μm glass filter to prepare acomposition for a light shielding pattern.

The surface tension of the composition for a light shielding pattern wasmeasured with a tension meter (Model PD-Z, manufactured by KyowaInterface Science Co., Ltd.) and found to be 37.5 mN/m.

This composition was blade-coated on the whole area of the exposedphotocatalyst-containing layer under conditions of blade interval 40 μmand speed 0.6 m/min. As shown in FIG. 7, the composition for a lightshielding pattern was repelled by the unexposed areas and wasselectively coated only in the exposed areas. Heating at 100° C. for 30min resulted in the formation of a lattice-like light shielding pattern119 through a photocatalyst layer 104 on a glass substrate 102.

Example A-9

A sodium ion block layer was prepared in the same manner as in ExampleA-3. Next, 3 g of isopropyl alcohol, 2.2 g of an organosilane (TSL8113,manufactured by Toshiba Silicone Co., Ltd.), 0.15 g of afluoroalkylsilane (MF-160E, manufactured by Tohchem ProductsCorporation: a 50 wt % isopropyl ether solution ofN-[3-(trimethoxysilyl)propyl]-N-ethylperfluorooctanesulfonamide), and0.2 g of titanium oxide powder (ST-21, average particle diameter 20 nm,manufactured by Ishihara Sangyo Kaisha Ltd.) were mixed together. Theresultant dispersion was stirred for 20 min while maintaining thetemperature at 100° C. The resultant dispersion was spin coated on thesubstrate with a sodium ion block layer formed thereon. The assembly wasdried at a temperature of 150° C. for 10 min, permitting hydrolysis andpolycondensation to proceed. Thus, a 3 μm-thick photocatalyst-containinglayer with a photocatalyst being strongly fixed in an organosiloxane wasformed. The average roughness of the surface of thephotocatalyst-containing layer was measured by the tracer method in thesame manner as in Example A-1 and found to be Ra=4 nm. Further, thephotocatalyst-containing layer was irradiated with ultraviolet light atan intensity of 70 mW/cm² for 5 min using a high pressure mercury lampthrough a lattice-like mask. In this case, the contact angle of thephotocatalyst-containing layer with water and n-octane was measured witha contact angle goniometer (Model CA-Z, manufactured by Kyowa InterfaceScience Co., Ltd.). The results are shown in Table A-4.

Example A-10

A sodium ion block layer was formed on a glass substrate in the samemanner as in Example A-3. A photocatalyst-containing layer was thenformed in the same manner as in Example A-9, followed by exposure in thesame manner as in Example A-9.

Unexposed areas and exposed areas were subjected to elementary analysisusing an X-ray photoelectron spectroscopic device (ESCALAB220-I-XL,manufactured by V. G. Scientific). Quantitative calculation wasconducted by Shirley's background correction and Scofield's relativesensitivity coefficient correction. The results were expressed in termsof relative value by presuming the weight of Si to be 100 and shown inTable A-1.

TABLE A-1 Si C O Ti F Unexposed area 100 98 179 21 40 Exposed area 10021 220 20 0

Table A-1 shows that exposure decreases the proportion of carbon andfluorine and increases the proportion of oxygen. As is apparent from theresults of Example A-9, since the photocatalyst-containing layer hasreduced contact angle with water, it is considered that organic groupsbonded to silicon atoms, such as methyl and fluoroalkyl groups, havebeen substituted by oxygen-containing groups, such as hydroxyl groups.

Example A-11

A sodium ion block layer was prepared in the same manner as in ExampleA-3. Next, 3 g of isopropyl alcohol, 0.4 g of an organosilane (TSL8113,manufactured by Toshiba Silicone Co., Ltd.), 0.75 g of afluoroalkylsilane (MF-160E, manufactured by Tohchem ProductsCorporation: a 50 wt % isopropyl ether solution ofN-[3-(trimethoxysilyl)propyl]-N-ethylperfluorooctanesulfonamide), and 2g of titanium oxide (titanium oxide coating liquid ST-K01, solid content10% by weight, manufactured by Ishihara Sangyo Kaisha Ltd.) were mixedtogether. The resultant dispersion was stirred for 60 min whilemaintaining the temperature at 100° C. The resultant dispersion was spincoated on the substrate with a sodium ion block layer formed thereon.The assembly was dried at a temperature of 150° C. for 10 min,permitting hydrolysis and polycondensation to proceed. Thus, a 3μm-thick photocatalyst-containing layer with a photocatalyst beingstrongly fixed in an organosiloxane was formed. Further, thephotocatalyst-containing layer was irradiated with ultraviolet light atan intensity of 70 mW/cm² for 10 min using a high pressure mercury lampthrough a lattice-like mask. In this case, the contact angle of thephotocatalyst-containing layer with water and n-octane was measured witha contact angle goniometer (Model CA-Z, manufactured by Kyowa InterfaceScience Co., Ltd.). The results are shown in Table A-4.

Example A-12

A 0.3 μm-thick photocatalyst-containing layer was formed in the samemanner as in Example A-4. The photocatalyst-containing layer wasirradiated with ultraviolet light at an intensity of 70 mW/cm² for 2 minusing a high pressure mercury lamp through a mask having light shieldinglayers provided at a pitch of 100 μm. A photosensitive resin compositionfor color pixels of a color filter was dropped by means of a dispenser(1500 XL, manufactured by EFD). As a result, the composition could wetand spread on exposed areas to form pixels.

Example A-13

3 g of isopropyl alcohol, 0.3 g of an organosilane (TSL8113,manufactured by Toshiba Silicone Co., Ltd.), 0.45 g of afluoroalkylsilane (MF-160E, manufactured by Tohchem ProductsCorporation: a 50 wt % isopropyl ether solution ofN-[3-(trimethoxysilyl)propyl]-N-ethylperfluorooctanesulfonamide), and 2g of titanium oxide (titanium oxide coating liquid ST-K01, solid content10% by weight, manufactured by Ishihara Sangyo Kaisha Ltd.) were mixedtogether. The resultant dispersion was stirred for 20 min whilemaintaining the temperature at 100° C. The resultant dispersion was spincoated on a 0.3 mm-thick aluminum sheet. The coated substrate was driedat a temperature of 150° C. for 10 min, permitting hydrolysis andpolycondensation to proceed. Thus, a 0.5 μm-thickphotocatalyst-containing layer with a photocatalyst being strongly fixedin an organosiloxane was formed.

The structure for pattern formation thus obtained was heated on a hotplate at various temperatures. In this state, heat rays were removedfrom light emitted from an ultrahigh pressure mercury lamp (UXM-3500,Model ML-40D lamp house, manufactured by Ushio Inc.), and onlyultraviolet light with wavelengths ranging from 241 nm to 271 nm wasapplied at an intensity of 8.1 mW/cm² for 300 sec. The contact angle ofthe photocatalyst-containing layer with water was measured with acontact angle goniometer (Model CA-Z, manufactured by Kyowa InterfaceScience Co., Ltd.). The results are shown in Table A-2. As is apparentfrom Table A-2, heating accelerated photocatalytic reaction.

TABLE A-2 Before exposure After exposure  25 130° 118°  60° C. 130°  40°100° C. 130° Below 5°

Example A-14

A photocatalyst-containing layer was formed on a quartz glass having asize of 10 cm in length×10 cm in width in the same manner as in ExampleA-3. A negative-working photomask with a light-permeable portion havinga size of 150 μm×300 μm disposed at intervals of 30 μm was brought tointimate contact with the structure for pattern formation or wasdisposed into the structure for pattern formation while leaving a spaceof 100 μm. Ultraviolet light with wavelengths ranging from 320 to 390 nmwas then applied using a high pressure mercury lamp at an intensity of70 mW/cm² for 2 min. The contact angle of the photocatalyst-containinglayer with water was measured with a contact angle goniometer (ModelCA-Z, manufactured by Kyowa Interface Science Co., Ltd.). The resultsare summarized in Table A-3.

TABLE A-3 Unexposed area Exposed area Intimate contact 113° Below 97°Leaving space of 100 μm 113° Below 5°

Example A-15

The negative-working photomask as described in Example A-14 was disposedon the structure for pattern formation while leaving a space of 100 μmin the same manner as in Example A-14. Exposure was performed in thesame manner as in Example A-14, except that the exposure was carried outwife spraying air onto exposing areas of the structure for patternformation. As a result, exposure for 70 sec provided a contact anglewith water of not more than 5°.

Example A-16

On a glass substrate having a size of 10 cm in length×10 cm in width×0.1cm in thickness were formed a primer layer and aphotocatalyst-containing layer in the same manner as in Example A-10.Ultraviolet light with wavelengths ranging from 320 nm to 390 nm wasthen applied at an intensity of 70 mW/cm² for 7 min from a high pressuremercury lamp through a photomask with a light shielding portion having asize of 100 μm in length×100 μm in width formed thereon at intervals of20 μm.

Next, an ink ribbon comprising a hot-melt ink composition layer havingthe following composition as a hot-melt ink layer provided on a 10μm-thick polyester film was brought to intimate contact with thepattern-wise exposed photocatalyst-containing layer. The assembly wasthen heated at 90° C., and the ink ribbon was then peeled off at a speedof 150 mm/sec and an angle of 70°.

Carbon black (#25, manufactured by Mitsubishi 20 pts. wt. ChemicalCorporation) Ethylene-vinyl acetate copolymer (manufactured 10 pts. wt.by DuPont-Mitsui Polychemicals Co., Ltd.) Carnauba wax 10 pts. wt.Paraffin wax (HNP-11, manufactured by Nippon 60 pts. wt. Seiro Co.,Ltd.)

As a result, the ink was not adhered to the unexposed areas of thestructure for pattern formation, and the ink could be transferred onlyonto the exposed areas to form a light shielding pattern.

Example A-17

On a glass substrate having a size of 10 cm in length×10 cm in width×0.1cm in thickness were formed a primer layer and aphotocatalyst-containing layer in the same manner as in Example A-10.Thus, a structure for pattern formation was prepared. Ultraviolet lightwith wavelengths ranging from 320 nm to 390 nm was then applied to thestructure for pattern formation at an intensity of 70 mW/cm² for 7 minfrom a high pressure mercury lamp through a photomask with a 5 μm-widthline provided thereon at the same intervals as the line width.

Next, the exposed structure for pattern formation was immersed in aliquid having a concentration of 12.5 ml/liter, prepared by diluting asensitizer liquid for chemical plating (S-10X for glass/ceramics,manufactured by C.Uyemura & Company Ltd.), at 25° C. while swinging for20 sec. After washing with water, the exposed structure for patternformation was immersed in a liquid having a concentration of 12.5ml/liter, prepared by diluting a reduction catalyst liquid (a palladiumcolloid catalyst A-10X, manufactured by C.Uyemura & Company Ltd.) at 25°C. while swinging for 20 sec and was then immersed with swinging for onehr in an electroless nickel plating solution (Nimuden LPX, manufacturedby C.Uyemura & Company Ltd.) at 80° C. Thus, a 0.5 μm-thick nickel layercould be formed on the exposed areas.

Further, the plated structure for pattern formation was immersed withswinging for 5 min in an electroless gold plating bath (ELGB511,manufactured by C.Uyemura & Company Ltd.) at 90° C. to form a 0.1μm-thick gold layer on the nickel pattern. The plated structure forpattern formation was then immersed with swinging for one hr in anelectroless gold plating bath for thick plating (GCBEL2M, manufacturedby C.Uyemura & Company Ltd.) at 60° C. to form a 2 μm-thick gold layer.

Example A-18

The same composition as described in Example A-4 was spin coated onto aquartz glass substrate having a size of 10 cm in length×10 cm inwidth×0.1 cm in thickness to form a 0.4 μm-thickphotocatalyst-containing layer. The photocatalyst-containing layer wasthen irradiated with ultraviolet light using a mercury lamp at anintensity of 70 mW/cm² for 90 sec through a photomask with a pattern ofrectangles having an opening size of 23 μm×12 μm. Thus, a transparentsubstrate comprising a photocatalyst-containing layer having thereon arectangular pattern with high surface free energy was obtained.

A thin layer of a perylene pigment having a chemical structurerepresented by formula A-4 was vacuum deposited onto the whole area ofthe transparent substrate under conditions of degree of vacuum 1×10⁻⁵Torr and deposition rate 1 nm/sec. The surface of the thin layer waswashed with acetone. As a result, the deposit was separated only fromthe unexposed areas due to the difference between the adhesion of thepigment to the exposed areas and the adhesion of the pigment to theunexposed areas. Thus, a rectangular pattern of red pigment with thesize of the rectangle being 23 μm×12 μm could be obtained.

Example A-19

The same composition as described in Example A-4 was spin coated onto a100 μm-thick polyimide film to form a 0.4 μm-thickphotocatalyst-containing layer. The photocatalyst-containing layer wasthen exposed to light using a mercury lamp at an intensity of 70 mW/cm²for 90 sec through a negative-working photomask having a circuit patternwritten in a width of 50 μm to form a transparent substrate comprising aphotocatalyst-containing layer having thereon a high surface energyportion.

Next, aluminum was vacuum deposited onto the whole area of thetransparent substrate under conditions of degree of vacuum 1×10⁻⁵ Torrand deposition rate 4 nm/sec. A cellophane pressure sensitive adhesivetape (JIS Z 1522, manufactured by Sekisui) was applied onto the surfaceof the thin layer of aluminum and then peeled off under conditions of135° and speed 300 mm/sec. As a result, the deposit layer was separatedonly from the unexposed areas due to the difference between the adhesionof the thin layer of aluminum to the transparent substrate in itsexposed areas and the adhesion of the thin layer of aluminum to thetransparent substrate in its unexposed areas, and a circuit patternhaving a circuit of 50 μm in width and 0.1 μm in layer thickness couldbe obtained.

Example A-20

The same composition as described in Example A-4 was spin coated onto aquartz glass substrate to form a 0.3 μm-thick photocaltayst-containinglayer. The photocatalyst-containing layer was then irradiated withultraviolet light using a mercury lamp at an intensity of 70 mW/cm² for2 min through a mask with an opening diameter of 5 mm.

Various liquids having known surface tension were dropped on thephotocatalyst-containing layer to measure the contact angle between thephotocatalyst-containing layer and the liquids with a contact anglegoniometer (Model CA-Z, manufactured by Kyowa Interface Science Co.,Ltd.), and the critical surface tension was determined by Zismanplotting. As a result, the critical surface tension was 14.6 mN/m forunexposed areas and was 72.3 mN/m for exposed areas.

Next, 100 parts by weight of a ultraviolet curable monomer (Beam Set770, manufactured by Arakawa Chemical Industries, Ltd.) and 5 parts byweight of a curing initiator (Irgacure 1700, manufactured by CibaSpecialty Chemicals, K.K.) were mixed together to prepare an ultravioletcurable composition.

The surface tension of the ultraviolet curable monomer composition wasmeasured with a tension meter (Model PD-Z, manufactured by KyowaInterface Science Co., Ltd.) and found to be 35 mN/m. Further, theviscosity was measured with a viscometer (CJV5000, manufactured byChichibu-Onoda) and found to be 4.3 mPa·sec. This ultraviolet curablemonomer was spin coated on the whole area of the exposedphotocatalyst-containing layer.

The ultraviolet curable monomer composition was repelled by theunexposed areas and was selectively coated only onto the exposed areas.Ultraviolet light was then applied using a high pressure mercury lamp anintensity of 70 mW/cm² for 3 min. As a result, a pattern of circles,with a diameter of 5 mm, of the ultraviolet cured resin was obtained.

Comparative Example A-1

A commercially available original plate for offset printing wasevaluated for properties using a thermal plate Pearl dry (manufacturedby Presstek) in the same manner as in Example A-3. The results aresummarized in Table A-4.

Comparative Example A-2

A waterless offset plate HGII (manufactured by Toray Industries, Inc.),a commercially available original plate for offset printing, wasevaluated for properties in the same manner as in Example A-3. Theresults are summarized in Table A-4.

Comparative Example A-3

A photocatalyst-containing layer was formed in the same manner as inExample A-4, except that the fluoroalkylsilane was not used. Thephotocatalyst-containing layer was evaluated for properties in the samemanner as in Example A-4. The results are summarized in Table A-4.

Comparative Example A-4

A sodium ion block layer was prepared in the same manner as in ExampleA-3. Next, 3 g of isopropyl alcohol, 2.2 g of an organosilane (TSL8113,manufactured by Toshiba Silicone Co., Ltd.), 0.15 g of afluoroalkylsilane (MF-160E, manufactured by Tohchem ProductsCorporation: a 50 wt % isopropyl ether solution ofN-[3-(trimethoxysilyl)propyl]-N-ethylperfluorooctanesulfonamide), and0.2 g of titanium oxide powder (ST-41, average particle diameter 50 nm,manufactured by Ishihara Sangyo Kaisha Ltd.) were mixed together. Theresultant dispersion was stirred for 20 min while maintaining thetemperature at 100° C. The resultant dispersion was spin coated on thesubstrate with a sodium ion block layer formed thereon. The assembly wasdried at a temperature of 150° C. for 10 min, permitting hydrolysis andpolycondensation to proceed. Thus, a 3 μm-thick photocatalyst-containinglayer with a photocatalyst being strongly fixed in an organosiloxane wasformed. The average roughness of the surface of thephotocatalyst-containing layer was measured by the tracer method in thesame manner as in Example A-1 and found to be Ra=30 nm. Further, thephotocatalyst-containing layer was irradiated with ultraviolet light atan intensity of 70 mW/cm² for 5 min using a high pressure mercury lampthrough a lattice-like mask. In this case, the contact angle of thephotocatalyst-containing layer with water and n-octane was measured witha contact angle goniometer (Model CA-Z, manufactured by Kyowa InterfaceScience Co., Ltd.). The results are summarized in Table A-4.

TABLE A-4 Exposed area Unexposed area Water n-Octane Water n-Octane Ex.A-3 Below 5° Below 5° 113° 16° Ex. A-4 Below 5° Below 5° 107° 47° Ex.A-7 Below 5° Below 5° 105° 40° Ex. A-9 Below 5° Below 5° 100° 30° Ex.A-11 Below 5° Below 5° 151° 77° Comp. Ex. A-1  84° Below 5° 105° 11°Comp. Ex. A-2 104° 5° 116° 13° Comp. Ex. A-3 Below  5° Below 5°  86° 10°Comp. Ex. A-4  10° 10° 105° 26°

Example A-21

A 20 wt % dimethylformamide solution of a composition for a primer layer(Kan-coat 90T-25-3094, manufactured by Kansai Paint Co., Ltd.) wascoated on a 0.15 mm-thick degreased aluminum sheet. The coated aluminumsheet was dried at 200° C. for 1 min. Thus, a 3 μm-thick primer layerwas formed.

Next, 3 g of isopropyl alcohol, 4.2 g of an organosilane (TSL8113,manufactured by Toshiba Silicone Co., Ltd.), and 0.2 g of titanium oxidepowder (ST-01, average particle diameter 7 nm, manufactured by IshiharaSangyo Kaisha Ltd.) were mixed together. The mixture was stirred for 60min while maintaining the temperature at 100° C. The resultantdispersion was spin coated onto the substrate having thereon a primerlayer. The assembly was dried at 150° C. for 5 min, permittinghydrolysis and polycondensation to proceed. Thus, a layer was formed.

Ultraviolet irradiation was carried out using a high pressure mercurylamp at an intensity of 70 mW/cm² for 10 min. In this case, the contactangle with water and n-octane was measured with a contact anglegoniometer (Model CA-Z, manufactured by Kyowa Interface Science Co.,Ltd.). The results are summarized in Table A-5.

TABLE A-5 Before irradiation After irradiation Water 72° 0° n-OctaneBelow 6° Below 5°

Further, the original plate for lithography using dampening water wasexposed to light from the above mercury lamp through a gradationpositive-working mask having halftone dots of 2 to 98% with 175lines/in. Thus, a pattern was formed.

Next, the printing plate thus obtained was mounted on an offset printingmachine (Alpha New Ace, manufactured by Alpha Giken K.K.), and printingwas carried out on a coated paper using a printing ink (ACROS(EIKUROSU)Deep Red, manufactured by The Inctec Inc.) and dampening water (a liquidprepared by diluting a clean etch liquid 20 times with water,manufactured by Nikken Chemicals Co., Ltd.) at a printing speed of 5000sheets/hr. As a result, 20,000 sheets of good prints could be obtained.

Example A-22

2.7 g of tetraethoxysilane Si(OC₂H₆)₄, 38.7 g of ethanol, and 4.5 g of 2N hydrochloric acid were mixed together. The mixture was stirred for 10min. The resultant solution was spin coated onto a substrate, and thecoated substrate was dried at 80° C. for 30 min. Thus, a 0.2 μm-thicksodium ion block layer was formed.

Tetraethoxysilane Si(OC₂H₅)₄ (0.62 g), 0.96 g of titania sol ((TA-15,manufactured by Nissan Chemical Industries Ltd.), 26.89 g of ethanol,and 0.32 g of pure water were mixed together. The mixture was stirredfor 10 min. The resultant dispersion was spin coated on the substratewith the sodium ion block layer formed thereon. The assembly was driedat a temperature of 150° C. for 30 min, permitting hydrolysis andpolycondensation to proceed. Thus, a 0.2 μm-thickphotocatalyst-containing layer, having high surface free energy, with aphotocatalyst being strongly fixed in silica was prepared as sample A-1.

Next, a solution of 5% by weight of an olive oil in cyclohexanone wasspin coated onto the photocatalyst-containing layer of sample A-1 at acoverage of 1 g/m². The coating was dried at a temperature of 80° C. for10 min to from an organic material layer having low surface free energy.Thus, sample A-2 was prepared.

Sample A-1 and sample A-2 were irradiated with ultraviolet light from amercury lamp at an intensity of 230 mW/cm² for 5 min. Thereafter, thecontact angle of the samples with water was measured with a contactangle goniometer (Model CA-Z, manufactured by Kyowa Interface ScienceCo., Ltd.). The results are summarized in Table A-6. As a result, it wasfound that, in sample A-2, the organic material layer was degraded andremoved by photocatalytic action and this brought sample A-2 to the samestate as sample A-1 which is the sample before coating. For sample A-1having a high critical surface tension layer, the wettability afterlight irradiation was substantially the same as the wettability beforelight irradiation.

TABLE A-6 Before irradiation After irradiation Sample A-1  8° 7° SampleA-2 47° 7°

Further, a 2 wt % aqueous solution of polyvinyl alcohol (Gosenol AH-26,manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was spincoated onto the surface of sample A-1 to a thickness of 0.2 μm. Thecoating was heated at 80° C. for 45 min to form a film. Subsequently,the film was irradiated with ultraviolet light from a mercury lamp at anintensity of 280 mW/cm² for 8 min. The contact angle of the film withwater was measured with a contact angle goniometer (Model CA-Z,manufactured by Kyowa Interface Science Co., Ltd.). As a result, thecontact angle before light irradiation and the contact angle after lightirradiation were 62° and not more than 5°, respectively.

Example A-23

A solution of 5% by weight of a mixture of 94.99% by weight ofpolydimethylsiloxane having a hydroxyl group at its both ends (degree ofpolymerization 700), 5% by weight of methyltriacetoxysilane, and 0.01%by weight of dibutyltin dilaurate in Isopar E (manufactured by ExxonChemical) was spin coated onto sample A-1 of Example A-22 to a thicknessof 0.2 μm. The coating was dried at 100° C. for 10 min to form a film.

The film was then irradiated with light from a mercury lamp at anintensity of 50 mW/cm² for one min. As a result, the wettability interms of the contact angle was changed from 130° to not more than 5°.

A 20 wt % dimethylformamide solution of a composition for a primer layer(Kan-coat 90T-25-3094, manufactured by Kansai Paint Co., Ltd) was coatedonto a degreased aluminum sheet having a thickness of 0.15 mm. Thecoated aluminum sheet was dried at 200° C. for one min to form a 3μm-thick primer layer.

Next, a photocatalyst-containing layer and a wettability-variablematerial layer as described in Example A-22 were formed onto the primerlayer to prepare an original plate for waterless plate.

Subsequently, a pattern was formed under conditions of Nd:YAG laser (355nm A-Physic Star Line) and recording energy 200 mJ/cm². The printingplate thus obtained was mounted on an offset printing machine (Alpha NewAce, manufactured by Alpha Giken K.K.), and printing was carried out ona coated paper using an ink for waterless printing (Inctec Waterless SDeep Blue, manufactured by The Inctec Inc.) at a printing speed of 5000sheets/hr. As a result, 20,000 sheets of good prints could be obtained.

Example A-24

A sodium block layer was formed on a soda-lime glass substrate having asize of 10 cm in length×10 cm in width×0.1 cm in thickness in the samemanner as in Example A-22. A solution prepared by mixing 1 g oftetraethoxytitanium (Ti(OC₂H₅)₄), 9 g of ethanol, and 0.1 g ofhydrochloric acid together was spin coated on the block layer.

The assembly was heated at 150° C. for 10 min to form a 0.1 μm-thickamorphous titania layer. The amorphous titania layer was heated at 400°C. for 10 min to create a phase change to an anatase form of titanialayer.

A wettability-variable layer was formed on the titania layer in the samemanner as in Example A-23 and then irradiated with light from a mercurylamp at an intensity of 50 mW/cm² through a chart mask having aresolution of 50 lp/mm for 2 min.

Next, an ink for waterless lithography (Inctec Waterless S Yellow,manufactured by The Inctec Inc.) was coated on the whole area of theexposed pattern forming structure by means of an RI tester (Model RI-2tester, manufactured by Ishikawajima Industrial Machinery Co., Ltd.). Asa result, a yellow pattern was obtained wherein the unexposed areasrepelled the ink due to its oil repellency with the ink selectivelycoated only on the exposed area.

Example A-25

A glass substrate provided with a sodium ion block layer was prepared inthe same manner as in Example A-1. Next, 0.14 g of a surfactant (BL-2,manufactured by Nihon Surfactant Kogyo K.K.), 0.62 g oftetraethoxysilane Si(OC₂H₅)₄, 0.96 g of a titania sol (TA-15,manufactured by Nissan Chemical Industries Ltd.), 26.89 g of ethanol,and 0.32 g of water were mixed together. The mixture was stinted for 10min. The resultant dispersion was spin coated on the substrate with the0.2 μm-thick sodium ion block layer formed thereon.

The assembly was then dried at a temperature of 150° C. for 30 min,permitting hydrolysis and polycondensation to proceed. Thus, a 0.2μm-thick photocatalyst-containing layer with a photocatalyst and asurfactant being strongly fixed in silica was formed. The sample thusobtained was irradiated with ultraviolet light from a xenon lamp at anintensity of 3 mW/cm². In this case, a change in contact angle betweenthe sample and water with the elapse of time was measured with a contactangle goniometer (Model CA-Z, manufactured by Kyowa Interface ScienceCo., Ltd.). The results are shown in FIG. 8. As is apparent from FIG. 8,the contact angle (63° before light irradiation) gradually decreasedwith the elapse of irradiation time and, about 80 min after theinitiation of irradiation, reached 6°.

Example A-26

3 g of Glasca HPC7002 (Japan Synthetic Rubber Co., Ltd.), a silica sol,and 1 g of HPC402H (Japan Synthetic Rubber Co., Ltd.), analkylalkoxysilane, were mixed together. The mixture was stirred for 5min. The resultant solution was spin coated on a 0.15 mm-thick aluminumsheet to form a 2 μm-thick primer layer.

Next, a photocatalyst-containing layer as described in Examples A-23 wasformed on the primer layer to obtain an original plate for a printingplate.

Further, the original plate for lithography using dampening water wasexposed to light from the above xenon lamp through a gradationpositive-working film having halftone dots of 2 to 98% with 175lines/in. Thus, a pattern was formed.

Next, the printing plate thus obtained was mounted on an offset printingmachine (Alpha New Ace, manufactured by Alpha Giken K. K.), and printingwas carried out on a coated paper using an offset printing ink(ACROS(EIKUROSU) Deep Red, manufactured by The Inctec Inc.) anddampening water at a printing speed of 5000 sheets/hr. As a result,20,000 sheets of good prints could be obtained.

Example A-27

A composition as described in Example A-4 was spin coated onto atransparent substrate of quartz glass to form a 0.4 μm-thickphotocatalyst-containing layer. Subsequently, the coating was irradiatedwith light from a mercury lamp at an intensity of 70 mW/cm² through amask having a circular pattern with a opening diameter of 9 mm for 90sec. Thus, a transparent substrate having thereon a highly wettablecircular pattern was obtained.

1000 g of a water-soluble ultraviolet curable ester acrylate resin(AQ-7, manufactured by Arakawa Chemical Industries, Ltd.), 50 g of acuring initiator (Irgacure 184, manufactured by Ciba SpecialtyChemicals, K.K.), and 25 g of water were mixed together. The mixture wasstirred for 3 min. 30 μl of the mixed liquid was dropped through amicrosyringe on the center of the circular pattern utilizing adifference in wettability formed on the transparent substrate.

Subsequently, light was applied from a mercury lamp at an intensity of70 mW/cm² for 10 sec. Thus, a lens having a diameter of 9 mm and a focallength of 45 mm was prepared.

Example A-28

A composition as described in Example A-4 was spin coated onto atransparent substrate of quartz glass to form a 0.4 μm-thickphotocatalyst-containing layer. Subsequently, the coating was irradiatedwith light from a mercury lamp at an intensity of 70 mW/cm² through amask having a circular pattern with a opening diameter of 1 mm for 90sec. Thus, a transparent substrate having thereon a highly wettablecircular pattern was obtained.

1000 g of a water-soluble ultraviolet curable ester acrylate resin(AQ-7, manufactured by Arakawa Chemical Industries, Ltd.), 50 g of acuring initiator (Irgacure 184, manufactured by Ciba SpecialtyChemicals, K.K.), and 125 g of water were mixed together. The mixturewas stinted for 3 m in. The mixed liquid was spin coated onto thecircular pattern utilizing a difference in wettability formed on thetransparent substrate to a thickness of 20 μm. As a result, the mixedliquid was deposited only onto the circular portion. Subsequently, lightwas applied from a mercury lamp at an intensity of 70 mW/cm² for 3 sec.Thus, a lens having a diameter of 1 mm and a focal length of 2.5 mm wasprepared.

Example A-29

A 20 wt % dimethylformamide solution of a primer (a primer paint formetals, Kan-coat 90T-25-3094, manufactured by Kansai Paint Co., Ltd.)was coated on a 0.23 mm-thick degreased aluminum sheet. The coatedaluminum sheet was dried at 200° C. for 1 min. Thus, a 3 μm-thick primerlayer was formed.

A composition comprising 9 g of polydimethylsiloxane of which both endshad been modified with OH(X-22-160AS, functional group equivalent 112,manufactured by The Shin-Etsu Chemical Co., Ltd.), 1 g of a crosslinkingagent (polyisocyanate, Coronate L, manufactured by Nippon PolyurethaneIndustry Co., Ltd.), 0.05 g of butyltin dilaurate, 1 g of titanium oxidepowder (ST-01, particle diameter 7 nm, Ishihara Sangyo Kaisha Ltd.), 5 gof 1,4-dioxane, and 5 g of isopropanol was coated onto the primer layer.The coating was dried at 120° C. for 2 min to form a 1 μm-thickphotocatalyst-containing layer. Thus, an original plate for a printingplate was obtained. The average roughness of the surface of thephotocatalyst-containing layer was measured by the tracer method andfound to be Ra=2 nm.

The original plate was then irradiated with an excimer laser at 248 nmat an intensity of 200 mJ/cm² to form a pattern and to induce aphotocatalytic reaction.

The contact angle of exposed areas with water and n-octane was measuredwith a contact angle goniometer (Model CA-Z, manufactured by KyowaInterface Science Co., Ltd.). A result, a difference in wettabilitycould be confirmed. The results of measurement are shown in Table A-7.

Example A-30

The printing plate prepared in Example A-29 was mounted on an offsetprinting machine (Komori Sprint Four Color Machine), and printing wascarried out using a printing ink (Dri-o-color Deep Blue ink,manufactured by Dainippoin Ink and Chemicals, Inc.) onto coated paper.As a result, good prints could be obtained.

Example A-31

A primer layer was formed onto a 0.23 mm-thick aluminum substrate in thesame manner as in Example A-29. Subsequently, a composition comprising 8g of polydimethylsiloxane of which both ends had been modified withOH(X-22-160AS, manufactured by The Shin-Etsu Chemical Co., Ltd.), 1 g ofpolydimethylsiloxane (KF96, manufactured by The Shin-Etsu Chemical Co.,Ltd.), 1 g of a crosslinking agent (polyisocyanate, Coronate L,manufactured by Nippon Polyurethane Industry Co., Ltd.), 0.05 g ofdibutyltin dilaurate, 1 g of titanium oxide powder (ST-01, particlediameter 7 nm, Ishihara Sangyo Kaisha Ltd.), 5 g of toluene, and 5 g ofisopropanol was coated onto the primer layer. The coating was dried at150° C. for 2 min to form a 1 aim-thick photocatalyst-containing layer.Thus, an original plate for a printing plate was obtained.

The average roughness of the surface of the photocatalyst-containinglayer was measured by the tracer method and found to be Ra=2 nm.

The original plate was then irradiated with an excimer laser at 248 nmat an intensity of 200 mJ/cm² to form a pattern and to induce aphotocatalytic reaction.

The contact angle of exposed areas with water and n-octane was measuredwith a contact angle goniometer (Model CA-Z, manufactured by KyowaInterface Science Co., Ltd.). Aa result, a difference in wettabilitycould be confirmed. The results of measurement are shown in Table A-7.

Further, in the same manner as in A-30, the printing plate thus preparedwas mounted on an offset printing machine (Komori Sprint Four ColorMachine), and printing was carried out using a printing ink (Dri-o-colorDeep Blue ink, manufactured by Dainippon Ink and Chemicals, Inc.) ontocoated paper. As a result, good prints could be obtained.

Example A-32

3 g of a silica sol (Glasca HPC7002, manufactured by Japan SyntheticRubber Co., Ltd.) and 1 g of an alkylalkoxysilane (HPC402H, manufacturedby Japan Synthetic Rubber Co., Ltd.) were mixed together, and themixture was stirred for 5 min. The resultant solution was spin coatedonto a glass substrate having an area of 7.5 cm² to form a 2 μm-thicksodium ion block layer.

Next, 3 g of isopropyl alcohol, 0.76 g of a silica sol (Glasca HPC7002,manufactured by Japan Synthetic Rubber Co., Ltd.), 0.25 g of analkylalkoxysilane (Glasca HPC402H, manufactured by Japan SyntheticRubber Co., Ltd.), and 0.15 g of a fluoroalkylsilane (MF-160E,manufactured by Tohchem Products Corporation: a 50 wt % isopropyl ethersolution ofN-[3-(trimethoxysilyl)propyl]-N-ethylperfluorooctanesulfonamide) weremixed together. The resultant dispersion was stirred for 20 min whilemaintaining the temperature at 100° C. Thereafter, 2 g of titanium oxide(ST-K01, a liquid for titanium oxide, solid content 10% by weight,manufactured by Ishihara Sangyo Kaisha Ltd.) was added thereto, followedby stirring for additional 30 min.

The resultant dispersion was spin coated on the substrate with a sodiumblock layer formed thereon. The assembly was dried at a temperature of150° C. for 10 min, permitting hydrolysis and polycondensation toproceed. Thus, a 3 μm-thick photocatalyst-containing layer with aphotocatalyst being strongly fixed by an organopolysiloxane was formed.

A dispersion prepared by mixing 1 g of polydimethylsiloxane of whichboth ends had been modified with OH(X-22-160AS, manufactured by TheShin-Etsu Chemical Co., Ltd.), 2 g of a silica sol (Glasca HPC7002,manufactured by Japan Synthetic Rubber Co., Ltd.), and 1 g of analkylalkoxysilane (HPC402H, manufactured by Japan Synthetic Rubber Co.,Ltd.) and stirring the mixture for 5 min was coated onto thephotocatalyst-containing layer. The coating was dried at a temperatureof 150° C. for 20 min. Thus, a pattern forming structure having a driedfilm thickness of 0.5 μm.

The average roughness of the surface of the pattern forming structurewas measured by the tracer method and found to be Ra=2 nm.

The pattern forming structure was then irradiated with a YAG laser at365 nm at an intensity of 200 mJ/cm² to form a pattern and to induce aphotocatalytic reaction.

The contact angle of exposed areas with water and n-octane was measuredwith a contact angle goniometer (Model CA-Z, manufactured by KyowaInterface Science Co., Ltd.). The results of measurement are shown inTable A-7.

In the same manner as in Example A-27, the original plate for a printingplate was mounted on an offset printing machine (Komori Sprint FourColor Machine), and printing was carried out using a printing ink(Dri-o-color Deep Blue ink, manufactured by Dainippon Ink and Chemicals,Inc.) onto coated paper. As a result, good prints could be obtained.

Example A-33

A primer layer was formed onto a 0.23 mm-thick aluminum substrate in thesame manner as in Example A-29. 0.76 g of an emulsion typepolydimethylsiloxane (an addition reaction type) (KM-768, effectivecomponent 30%, manufactured by The Shin-Etsu Chemical Co., Ltd.), 1.34 gof water, 1 g of a titanium oxide sol (STS-01, particle diameter 7 nm,manufactured by Ishihara Sangyo Kaisha Ltd.), 0.008 g of a catalyst foran addition reaction (PM-6A), and 0.012 g of a catalyst for an additionreaction (PM-6B) were mixed together. The mixture was coated onto theprimer layer. The coating was dried at 160° C. for one min to form a 1μm-thick photocatalyst-containing layer.

A mask was brought to an intimate contact with thephotocatalyst-containing layer, followed by ultraviolet irradiation froma high pressure mercury lamp at an intensity of 70 mW/cm² for 10 min toconduct a photocatalytic reaction. Thereafter, the contact angle of thesample with water and n-octante was measured with a contact anglegoniometer (Model CA-Z, manufactured by Kyowa Interface Science Co.,Ltd.). The results are shown in Table A-7.

Example A-34

A 20 wt % dimethylformamide solution of a primer (a primer paint formetals, Kan-coat 90T-25-3094, manufactured by Kansai Paint Co., Ltd.)was coated on a 0.23 mm-thick degreased aluminum sheet. The coatedaluminum sheet was dried at 200° C. for 1 min. Thus, a 3 μm-thick primerlayer was formed.

3 g of a silica sol (Glasca HPC7002, manufactured by Japan SyntheticRubber Co., Ltd.) and 1 g of an alkylalkoxysilane (HPC402H, manufacturedby Japan Synthetic Rubber Co., Ltd.) were mixed together, and themixture was stirred by means of a stirrer for 5 mil. The resultantsolution was blade coated onto the primer layer. The coating was driedat 100° C. for 10 min.

Next, 3 g of isopropyl alcohol, 0.75 g of a silica sol (Glasca HPC7002,solid content 12%, manufactured by Japan Syntlhetic Rubber Co., Ltd.),0.25 g of an alkoxysilane (HPC402H, solid content 50%, manufactured byJapan Synthetic Rubber Co., Ltd.), 0.15 g of a fluoroalkylsilane(MF-160E, manufactured by Tohchem Products Corporation: a 50 wt %isopropyl ether solution ofN-[3-(trimethoxysilyl)propyl]-N-ethylperfluorooctanesulfonamide), and0.15 g of diethoxydimethylsilane (TSL8112, manufactured by ToshibaSilicone Co., Ltd.) were mixed together. The resultant solution wasstirred for 20 min while maintaining the temperature at 100° C.Thereafter, 2 g of a liquid for coating of titanium oxide (ST-K01, solidcontent 10%, manufactured by Ishihara Sangyo Kaisha Ltd.) was addedthereto, followed by stirring for additional 30 min. The resultantdispersion was spin coated. The coating was dried at a temperature of150° C. for 10 min, permitting hydrolysis and polycondensation toproceed. Thus, a 3 μm-thick photocatalyst-containing layer with aphotocatalyst being strongly fixed by an organopolysiloxane was formedto obtain a structure for pattern formation. The content ofdimethylsiloxane unit in the formed layer was 40%. The surface roughnessof the pattern forming structure was measured by the tracer method andfound to be Ra=2 nm.

The pattern forming structure was then irradiated with ultraviolet lightfrom a high pressure mercury lamp at an intensity of 70 mW/cm² through alattice-like mask for 5 min. The contact angle of the sample with waterand n-octane was measured with a contact angle goniometer (Model CA-Z,manufactured by Kyowa Interface Science Co., Ltd.). The results ofmeasurement are shown in Table A-7. The pattern forming structure with apattern formed thereon was mounted on an offset printing machine (KomoriSprint Four Color Machine), and printing was carried out using an inkfor waterless printing (Dri-o-color Deep Blue ink, manufactured byDainippon Ink and Chemicals, Inc.) onto coated paper. As a result, goodprints could be obtained.

Example A-35

A YAG laser at 355 nm was pattern-wise applied at an intensity of 200mJ/cm² onto a pattern forming structure prepared as described in ExampleA-34 to conduct a photocatalytic reaction. The contact angle of exposedareas with water and n-octane was measured with a contact anglegoniometer (Model CA-Z, manufactured by Kyowa Interface Science Co.,Ltd.). The results of measurement are shown in Table A-7.

The pattern forming structure with a pattern formed thereon was mountedon an offset printing machine (Komori Sprint Four Color Machine), andprinting was carried out using an ink for waterless printing(Dri-o-color Deep Blue ink, manufactured by Dainippon Ink and Chemicals,Inc.) onto coated paper. As a result, good prints could be obtained.

Example A-36

A pattern forming structure was prepared in the same manner as inExample A-31, except that the amount of diethoxydimethylsilane (TSL8112,manufactured by Toshiba Silicone Co., Ltd.) used in thephotocatalyst-containing layer was changed to 0.03 g and the content ofthe dimethylsiloxane unit was changed to 10%. The pattern formingstructure thus obtained was evaluated in the same manner as in ExampleA-31. The results are shown in Table A-7.

Printing was carried out on coated paper in the same manner as inExample A-31. As a result, good prints free from smudges could beobtained.

Example A-37

A 20 wt % dimethylformamide solution of a primer (a primer paint formetals, Kan-coat 90T-25-3094, manufactured by Kansai Paint Co., Ltd.)was coated on a 0.23 mm-thick degreased aluminum sheet. The coatedaluminum sheet was dried at 200° C. for 1 min. Thus, a 3 μm-thick primerlayer was formed.

3 g of a silica sol (Glasca HPC7002, manufactured by Japan SyntheticRubber Co., Ltd.) and 1 g of an alkylalkoxysilane (HPC402H, manufacturedby Japan Synthetic Rubber Co., Ltd.) were mixed together, and themixture was stirred by means of a stirrer for 5 min. The resultantsolution was blade coated onto the primer layer. The coating was driedat 100° C. for 10 min.

Next, 3 g of isopropyl alcohol, 0.75 g of a silica sol (Glasca IHPC7002,manufactured by Japan Synthetic Rubber Co., Ltd.), 0.25 g of analkylalkoxysilane (HPC402H, manufactured by Japan Synthetic Rubber Co.,Ltd.), 0.15 g of a fluoroalkylsilane (MF-160E, manufactured by TohchemProducts Corporation: a 50 wt % isopropyl ether solution ofN-[3-(trimethoxysilyl)propyl]-N-ethylperfluorooctanesulfonamide), and0.30 g of diethoxydimethylsilane were mixed together. The resultantsolution was stirred for 20 min while maintaining the temperature at100° C. Thereafter, 2 g of a liquid for coating of titanium oxide(ST-K01, solid content 10%, manufactured by Ishihara Sangyo Kaisha Ltd.)was added thereto, followed by stirring for additional 30 min. Theresultant dispersion was spin coated.

A dispersion prepared by mixing 3 g of isopropyl alcohol, 3 g of asilica sol (Glasca HPC7002, manufactured by Japan Synthetic Rubber Co.,Ltd.), and 1 g of an alkylalkoxysilane (HPC402H, manufactured by JapanSynthetic Rubber Co., Ltd.) and stirring the mixture for 5 min wascoated on the coating to form a 0.2 μm-thick coating. Thus, a patternforming structure was prepared.

The pattern forming structure was then exposed to a YAG laser at anenergy density of 200 mJ/cm² through a lattice-like mask to form apattern. Thus, a printing plate was prepared. The contact angle of thesample thus obtained with water and n-octane was measured with a contactangle goniometer (Model CA-Z, manufactured by Kyowa Interface ScienceCo., Ltd.). The results of measurement are shown in Table A-7.

The pattern forming structure with a pattern formed thereon was mountedon an offset printing machine (Komori Sprint Four Color Machine), andprinting was carried out using an ink for waterless printing(Dri-o-color Deep Blue ink, manufactured by Dainippon Ink and Chemicals,Inc.) onto coated paper. As a result, good prints could be obtained.

Comparative Example A-5

A machine plate was prepared in the same manner as in Example A-29,except that the substrate was not treated with the primer. The plate wasmounted on a printing machine in the same manner as in Example A-30. Asa result, the photocatalyst-containing layer, as partially separatedfrom the aluminum substrate, indicating that the adhesion of thephotocatalyst-containing layer to the substrate was unsatisfactory.Further, the plate was crosscut with a cutter, and a peeling test wascarried out using a mending tape (Scotch Mending Tape, manufactured bySumitomo 3M Ltd.). As a result, the plate provided with a primer layerwas free from the separation of the photocatalyst-containing layer,whereas the plate not provided with any primer layer caused theseparation of the photocatalyst-containing layer.

Comparative Example A-6

A commercially available original plate for offset printing wasevaluated for properties using a thermal plate Pearl dry (manufacturedby Presstek) in the same manner as in Example A-29. The results areshown in Table A-7.

Comparative Example A-7

A waterless offset plate HGII (manufactured by Toray Industries, Inc.),a commercially available original plate for offset printing, wasevaluated for properties in the same manner as in Example A-29. Theresults are shown in Table A-7.

Comparative Example A-8

A pattern forming structure was prepared in the same manner as inExample A-34, except that the amount of diethoxydimethylsilane (TSL8112,manufactured by Toshiba Silicone Co., Ltd.) used in thephotocatalyst-containing layer was changed to 0.2 g and the content ofthe dimethylsiloxane unit was changed to 50%. The roughness of thesurface of the photocatalyst-containing layer was measured by the tracermethod and found to be Ra=500 nm, indicating that the surface of thephotocatalyst-containing layer is rough. This high roughness made itimpossible to prepare a plate for printing.

Comparative Example A-9

A pattern forming structure was prepared in the same manner as inExample A-31, except that the amount of diethoxydimethylsilane (TSL8112,manufactured by Toshiba Silicone Co., Ltd.) used in thephotocatalyst-containing layer was changed to 0.01 g and the content ofthe dimethylsiloxane unit was changed to 5%. The pattern formingstructure was evaluated in the same manner as in Example A-31. Theresults are shown in Table A-7. Further, the surface roughness wasmeasured by the tracer method and found to be Ra=50 nm.

Printing was carried out on coated paper in the same manner as inExample A-34. As a result, smudges occurred.

TABLE A-7 Exposed area Unexposed area Water n-Octane Water n-Octane Ex.A-29 Below 5° Below 5° 113° 16° Ex. A-31 Below 5° Below 5° 113° 16° Ex.A-32 Below 5° Below 5° 115° 15° Ex. A-33 Below 5° Below 5° 107° 15° Ex.A-34 Below 5° Below 5° 113° 16° Ex. A-35 Below 80° Below 5° 113° 16° Ex.A-36 Below 70° Below 5° 113° 16° Ex. A-37 Below 60° Below 5° 115° 15°Comp. Ex. A-6  84° Below 5° 105° 11° Comp. Ex. A-7 104° Below 5° 116°13° Comp. Ex. A-9  80° Below 5° 115° 20°

In the pattern forming structures according to the first invention A, aphotocatalyst-containing layer is provided on a substrate. By virtue ofthis construction, a pattern can be formed by varying the wettability ofthe surface of the substrate through photocatalytic action created inresponse to light irradiation. This can realize the formation of apattern without development and other steps. Therefore, the patternforming structures according to the present invention can be used for awide variety of applications including original plates for printingplates and functional elements.

The following examples demonstrates use of a photocatalyst-containinglayer as a wettability-variable component layer.

Example B-1 Preparation of Composition for Photocatalyst-ContainingLayer

A coating liquid for a photocatalyst-containing layer (a composition fora photocatalyst-containing layer) was prepared according to thefollowing formulation.

(Formulation of Composition for Photocatalyst-containing Layer)

Photocatalyst-containing composition (ST-K01, 2 pts. wt. manufactured byIshihara Sangyo Kaisha Ltd.) Organoalkoxysilane (TSL8113, manufactured0.4 pt. wt. by Toshiba Silicone Co., Ltd. Fluoroalkylsilane (MF-160E,manufactured 0.3 pt. wt. by Tohchem Products Corporation) Isopropylalcohol 3 pts. wt.

This composition for a photocatalyst-containing layer was spin coatedonto a transparent substrate of soda-glass. The coating was dried at atemperature of 150° C. for 10 min, permitting hydrolysis andpolycondensation to proceed. Thus, a transparentphotocatalyst-containing layer (thickness 0.5 μm) with a photocatalystbeing strongly fixed in an organopolysiloxane was formed. Thephotocatalyst-containing layer was pattern-wise exposed to light from amercury lamp (wavelength 365 nm) at an intensity of 70 mW/cm² through amask for 50 sec. The contact angle of exposed areas and unexposed areaswith water was measured with a contact angle goniometer (Model CA-Z,manufactured by Kyowa Interface Science Co., Ltd.). In this case, awater droplet was dropped on the sample through a microsyringe, and 30sec after that, the contact angle was measured. As a result, the contactangle of the unexposed areas with water was 142°, while the contactangle of the exposed areas with water was not more than 10°. Thisconfirms that the exposed areas function as high critical surfacetension areas and a pattern can be formed by utilizing a difference inwettability between the exposed areas and the unexposed areas.

Formation of Black Matrix

A photocatalyst-con g layer was formed on a transparent substrate in thesame manner as described above (corresponding to FIG. 17 (A)).

The photocatalyst-containing layer was irradiated with light from amercury lamp (wavelength 365 nm) at an intensity of 70 mW/cm² for 50 seethrough a mask for a black matrix having a matrix-like opening pattern(opening line width 30 μm) so that exposed areas had high criticalsurface tension (not more than 10° in terms of contact angle with water)(corresponding to FIG. 17 (B)).

Separately, a mixture having the following composition was dissolved byheating at 90° C., centrifuged at 12,000 rpm, and then filtered througha 1-μm glass filter. 1% by weight of ammonium dichromate as acrosslinking agent was added to the resultant aqueous colored resinsolution to prepare a coating liquid for a black matrix (a black matrixcomposition).

(Black matrix composition) Carbon black (#950, manufactured by   4 pts.wt. Mitsubishi Chemical Corporation) Polyvinyl alcohol (Gosenol AH-26,manufactured by  0.7 pt. wt. Nippon Synthetic Chemical Industry Co.,Ltd.,) Ion-exchanged water 95.3 pts. wt.

Next, the coating liquid for a black matrix (black matrix composition)was blade coated onto the whole area of the photocatalyst-containinglayer. As a result, the black matrix composition was repelled by theunexposed areas in the photocatalyst-containing layer and selectivelycoated only onto the exposed areas. Thereafter, the assembly was driedat 60° C. for 3 min and then exposed to light from a mercury lamp tocure the black matrix composition, followed by heat treatment at 150° C.for 30 min to form a black matrix (corresponding to FIG. 17 (C)).

Formation of Colored Layer

At the outset, each mixture having the following composition was milledand dispersed by means of a triple roll mill, centrifuged at 12,000 rpm,and then filtered through a 1-μm glass filter. 1% by weight of ammoniumdichromate as a crosslinking agent was added to the resultant aqueouscolored resin solutions to prepare a composition for a red pattern, acomposition for a green pattern, and a composition for a blue pattern.

(Formulation of composition for red pattern) C.I. Pigment Red 168 1 pt.wt. 5 wt % aqueous solution of polyvinyl alcohol 10 pts. wt. (averagedegree of polymerization of polyvinyl alcohol 1750, degree ofsaponification 88 mol %) (Formation of composition for green pattern)C.I. Pigment Green 36 1 pt. wt. 5 wt % aqueous solution of polyvinylalcohol 10 pts. wt. (average degree of polymerization of polyvinylalcohol 1750, degree of saponification 88 mol %) (Formation ofcomposition for blue pattern). C.I. Pigment Blue 60 1 pt. wt. 5 wt %aqueous solution of polyvinyl alcohol 10 pts. wt. (average degree ofpolymerization of polyvinyl alcohol 1750, degree of saponification 88mol %)

Next, a red pattern forming region in the photocatalyst-containing layerwith the black matrix formed thereon was irradiated with light at anintensity of 70 mW/cm² for 50 sec from a mercury lamp (wavelength 365nm) through a mask having an opening pattern for a colored layer havinga size of 150 μm×300 μm so that exposed areas had high critical surfacetension (not more than 10° in terms of contact angle with water)(corresponding to FIG. 17 (D)).

The composition for a red pattern was then blade coated onto the wholearea of the photocatalyst-containing layer. As a result, the compositionfor a red pattern was repelled by unexposed areas in thephotocatalyst-containing layer and selectively coated only onto exposedareas. The assembly was then dried at 60° C. for 3 min and exposed tolight from a mercury lamp to cure the composition for a red pattern,followed by heat treatment at 150° C. for 30 min. Thus, a red patternwas formed (corresponding to FIG. 17 (E)).

Similarly, a green pattern forming region in thephotocatalyst-containing layer was irradiated with light, and thecomposition for a green pattern was selectively coated only onto exposedareas, followed by curing treatment and heat treatment to form a greenpattern. Further, similarly, a blue pattern forming region in thephotocatalyst-containing layer was irradiated with light, and thecomposition for a blue pattern was selectively coated only onto exposedareas, followed by curing treatment and heat treatment to form a bluepattern.

Subsequently, a two component mixing type thermosetting agent (SS7265,manufactured by Japan Synthetic Rubber Co., Ltd.) was spin coated as aprotective layer onto the colored layer. The coating was cured at 200°C. for 30 min to form a protective layer. Thus, a color filter of thepresent invention as shown in FIG. 13 was produced (corresponding toFIG. 17 (F)).

Example B-2 Preparation of Composition for Photocatalyst-containingLayer

A composition for a photocatalyst-containing layer was preparedaccording to the following formulation.

(Formulation of Composition for Photocatalyst-containing Layer)

Photocatalyst-containing formulation (STS-01, 1 pt. wt. manufactured byIshihara Sangyo Kaisha Ltd.) Reactive silicone (KM-768, manufactured by0.76 pt. wt. The Shin-Etsu Chemical Co., Ltd) Catalyst(CAT-PM6A:CAT-PM6B = 4:6, 0.02 pt. wt. manufactured by The Shin-EtsuChemical Co., Ltd) Water 1.34 pts. wt.

This composition for a photocatalyst-containing layer was spin coatedonto a transparent substrate of soda-lime glass. The coating was heattreated at a temperature of 160° C. for 1 min. Thus, a transparentphotocatalyst-containing layer (thickness 0.5 μm) with a photocatalystbeing strongly fixed in an organopolysiloxane was formed. Thephotocatalyst-containing layer was pattern-wise exposed to light from amercury lamp (wavelength 365 nm) at an intensity of 70 mW/cm² through amask for 100 sec. The contact angle of exposed areas and unexposed areaswith water was measured in the same manner as in Example B-1. As aresult, the contact angle of unexposed areas with water was 115°, whilethe contact angle of exposed areas with water was not more than 10°.This confirms that the exposed areas function as high critical surfacetension areas and a pattern can be formed by utilizing a difference inwettability between the exposed areas and the unexposed areas.

Formation of Black Matrix

A photocatalyst-containing layer was formed in the same manner asdescribed above. The photocatalyst-containing layer in its black matrixforming region was irradiated with light from a mercury lamp (wavelength365 nm) at an intensity of 70 mW/cm² for 100 sec. The black matrixcomposition was selectively coated only onto the exposed areas, followedby heat treatment to form a black matrix (corresponding to FIGS. 17 (A)to (C)).

Formation of Colored Layer

Pigment Red 168, Pigment Green 36, and Pigment Blue 60 were provided aspigments. Coating liquids for respective color patterns were preparedusing these pigments according to the following formulation.

(Formulation of Compositions for Color Patterns)

Pigment 3 pts. wt. Nonionic surfactant (NIKKOL BO-10TX, 0.05 pt. wt.manufactured by Nikko Chemicals Co., Ltd.) Polyvinyl alcohol (Shin-EtsuPoval AT, 0.6 pt. wt. manufactured by The Shin-Etsu Chemical Co., Ltd)Water 97 pts. wt.

Next, the whole area of the photocatalyst-containing layer with theblack matrix formed thereon was irradiated with light at an intensity of70 mW/cm² for 100 sec from a mercury lamp (wavelength 365 nm) so thatexposed areas had high critical surface tension (not more than 100 interms of contact angle with water).

Subsequently, the composition for a red pattern was dropped as dotshaving a diameter of 120 μm on the center portion of each red patternforming region surrounded by the black matrix through a nozzle.Similarly, the composition for a green pattern was dropped as dotshaving a diameter of 120 μm on the center portion of each green patternforming region surrounded by the black matrix through a nozzle. Further,the composition for a blue pattern was dropped as dots having a diameterof 120 μm on the center portion of each blue pattern forming regionsurrounded by the black matrix through a nozzle. The compositions forrespective color pattern, which had been dropped, were repelled by theblack matrix and homogeneously diffused in and selectively depositedonto respective color pattern forming regions having high criticalsurface tension surrounded by the black matrix. Thereafter, the assemblywas heat treated at 100° C. for 45 min. Thus, a colored layer comprisinga red pattern, a green pattern, and a blue pattern was formed.

A two component thermosetting agent (SS7265, manufactured by JapanSynthetic Rubber Co., Ltd.) was then spin coated as a protective layeronto the colored layer. The coating was cured at 200° C. for 30 min toform a protective layer. Thus, a color filter of the present inventionhaving a construction as shown in FIG. 13 was produced.

Example B-3 Formation of Photocatalyst-containing Layer

A composition for a photocatalyst-containing layer as described inExample B-1 was spin coated onto a transparent substrate of soda glasshaving a black matrix of a thin layer pattern having an opening size of90 μm×300 μm and a line width of 30 μm. The coated substrate was driedat a temperature of 150° C. for 10 min, permitting hydrolysis andpolycondensation to proceed. Thus, a transparentphotocatalyst-containing layer (thickness 0.5 μm) with a photocatalystbeing strongly fixed in an organopolysiloxane was formed (correspondingto FIG. 18 (A)).

Formation of Colored Layer

Next, the photocatalyst-containing layer was irradiated with light at anintensity of 70 mW/cm² for 50 sec from a mercury lamp (wavelength 365nm) through a mask for a red pattern so that exposed areas had highcritical surface tension (not more than 10° in terms of contact anglewith water (corresponding to FIG. 18 (B)). Separately, 1 g of C.I.Pigment Red 168 was mixed into 10 g of an aqueous solution prepared bydiluting an aqueous emulsion silicone (K-768, manufactured by TheShin-Etsu Chemical Co., Ltd.) three times with water. The mixture wasmilled and dispersed by means of a triple roll mill, centrifuged at12,000 rpm, and then filtered through a 1-μm glass filter. 0.1 g of acuring catalyst (Catalyst PM-6A:Catalyst PM-6B=4; 6 (manufactured by TheShin-Etsu Chemical Co., Ltd.)) was added to the aqueous colored resinsolution to prepare a coating liquid (a thermosetting resin composition)for a red pattern.

Next, the composition for a red pattern was bar coated onto the wholearea of the photocatalyst-containing layer. As a result, the compositionfor a red pattern was repelled by the photocatalyst-containing layer inits unexposed areas and selectively deposited only onto exposed areas.Thereafter, the coating was cured at 160° C. for 30 sec. Thus, a redpattern was formed (corresponding to FIG. 18 (C)).

Next, the photocatalyst-containing layer with a red pattern formedthereon was irradiated with light at an intensity of 70 mW/cm² for 50sec from a mercury lamp (wavelength 365 nm) through a mask for a bluepattern so that exposed areas had high critical surface tension (notmore than 10° in terms of contact angle with water).

Separately, 1 g of C.I. Pigment Blue 60 was mixed into 10 g of anaqueous solution prepared by diluting an aqueous emulsion silicone(K-768, manufactured by The Shin-Etsu Chemical Co., Ltd.) three timeswith water. A coating liquid (a thermosetting resin composition) for ablue pattern was prepared in the same manner as described above inconnection with the coating liquid for a red pattern.

Next, the composition for a blue pattern was bar coated onto the wholearea of the photocatalyst-containing layer. As a result, the compositionfor a blue pattern was repelled by the red pattern areas and thephotocatalyst-containing layer in its unexposed areas and selectivelydeposited only onto exposed areas. Thereafter, the coating was cured at160° C. for 30 sec. Thus, a blue pattern was formed.

Further, the photocatalyst-containing layer having thereon a red patternand a blue pattern was irradiated with light at an intensity of 70mW/cm² for 50 sec from a mercury lamp (wavelength 365 nm) through a maskfor a green pattern so that exposed areas had high critical surfacetension (not more than 10° in terms of contact angle with water).

Separately, 1 g of Lionol Green 2Y-301 (manufactured by Toyo InkManufacturing Co., Ltd.) was mixed into 10 g of a 10 wt % aqueoussolution of polyvinyl alcohol (average degree of polymerization 1750,degree of saponification 88 mol %). The mixture was milled and dispersedby means of a triple roll mill, centrifuged at 12,000 rpm, and thenfiltered through a 1-μm glass filter. 1% by weight of ammoniumdichromate as a crosslinking agent was added to the resultant aqueouscolored resin solutions to prepare a coating liquid (a photosensitiveresin composition) for a green pattern.

Next, the composition for a green pattern was bar coated onto the wholearea of the photocatalyst-containing layer. As a result, the compositionfor a green pattern was repelled by the red pattern areas, the bluepattern areas, and the photocatalyst-containing layer in its unexposedareas and selectively deposited only onto exposed areas. Thereafter, theassembly was dried at 60° C. for 3 min and then exposed to light from amercury lamp to cure the composition for a green pattern and, at thesame time, to bring the photocatalyst-containing layer to a highcritical surface tension state. Subsequently, heat treatment was carriedout at 150° C. for 30 min to form a green pattern.

Next, a two component thermosetting agent (SS7265, manufactured by JapanSynthetic Rubber Co., Ltd.) was spin coated as a protective layer ontothe colored layer. The coating was cured at 200° C. for 30 min to form aprotective layer. Thus, a color filter of the present invention having aconstruction as shown in FIG. 14 was produced.

Example B-4 Formation of Photocatalyst-containing Layer

A composition for a photocatalyst-containing layer as described inExample B-1 was spin coated onto a transparent substrate of soda glasshaving a black matrix of a thin layer pattern of chromium having anopening size of 140 μm×260 μm and a line width of 30 μm. The coatedsubstrate was dried at a temperature of 150° C. for 10 min, permittinghydrolysis and polycondensation to proceed. Thus, a transparentphotocatalyst-containing layer (thickness 0.5 μm) with a photocatalystbeing strongly fixed in an organopolysiloxane was formed (correspondingto FIG. 18 (A)).

Formation of Colored Layer

Next, a mask having a light shielding pattern (pattern pitch 155 μm×275μm) with the line width (20 μm) being smaller than the line width (30μm) of the black matrix was registered with the black matrix, and thephotocatalyst-containing layer was irradiated with light from a mercurylamp (wavelength 365 nm) through the mask at an intensity of 70 mW/cm²for 50 see so that exposed areas had high critical surface tension (notmore than 10° in terms of contact angle with water) (see FIG. 19).

Each of the exposed areas (high critical surface tension areas) had asize of 150 μm×270 μm, and the unexposed areas existed in a width of 20μm on the black matrix.

Pigment Red 168, Pigment Green 36, and Pigment Blue 60 were thenprovided as pigments. Coating liquids for respective color patterns wereprepared using these pigments according to the following formulation.

(Formulation of Compositions for Color Patterns)

Pigment 3 pts. wt. Nonionic surfactant (NIKKOL BO-10TX, 0.05 pt. wt.manufactured by Nikko Chemicals Co., Ltd.) Polyvinyl alcohol (Shin-EtsuPoval AT, 0.6 pt. wt. manufactured by The Shin-Etsu Chemical Co., Ltd)Water 97 pts. wt.

Subsequently, the composition for a red pattern was dropped as dotshaving a diameter of 120 μm on the center portion of each red patternforming region surrounded by the black matrix through a nozzle.Similarly, the composition for a green pattern was dropped as dotshaving a diameter of 120 μm on the center portion of each green patternforming region surrounded by the black matrix through a nozzle. Further,the composition for a blue pattern was dropped as dots having a diameterof 120 μm on the center portion of each blue pattern forming regionsurrounded by the black matrix through a nozzle. The compositions forrespective color patterns, which had been dropped, were repelled by theunexposed areas on the black matrix and homogeneously diffused in andselectively deposited onto respective color pattern forming regionshaving high critical surface tension surrounded by the black matrix.Thereafter, the assembly was heat treated at 100° C. for 45 min. Thus, acolored layer comprising a red pattern, a green pattern, and a bluepattern was formed.

A two component thermosetting agent (SS7265, manufactured by JapanSynthetic Rubber Co., Ltd.) was then spin coated as a protective layeronto the colored layer. The coating was cured at 200° C. for 30 min toform a protective layer. Thus, a color filter of the present inventionhaving a construction as shown in FIG. 14 was produced.

Example B-5 Formation of Photocatalyst-containing Layer

A composition for a photocatalyst-containing layer as described inExample B-1 was spin coated onto a transparent substrate of soda glasshaving a black matrix of a thin layer pattern having an opening size of90 μm×300 μm and a line width of 30 μm. The coated substrate was driedat a temperature of 150° C. for 10 min, permitting hydrolysis andpolycondensation to proceed. Thus, a transparentphotocatalyst-containing layer (thickness 0.5 μm) with a photocatalystbeing strongly fixed in an organopolysiloxane was formed.

Formation of Colored Layer

Pigment Red 168, Pigment Green 36, and Pigment Blue 60 were firstprovided as pigments. Each mixture having the following composition wasmilled and dispersed by means of a triple roll mill, centrifuged at12,000 rpm, and then filtered through a 1-μm glass filter. 1% by weightof ammonium dichromate as a crosslinking agent was added to theresultant aqueous colored resin solutions to prepare a coating liquidfor a red pattern, a coating liquid for a green pattern, and a coatingliquid for a blue pattern (photosensitive resin compositions).

(Formulation of Mixtures)

Pigment 1 pt. wt. 10 wt % aqueous solution of polyvinyl alcohol 10 pts.wt. (average degree of polymerization of polyvinyl alcohol 1750, degreeof saponification 88 mol %)

A photocatalyst-containing layer was formed onto thephotocatalyst-containing layer with a black matrix formed thereon in thesame manner as in Example B-1. The photocatalyst-containing layer wasirradiated with light from a mercury lamp (wavelength 365 nm) at anintensity of 70 mW/cm² for 50 sec through a mask for a red pattern tobring exposed areas to a high critical surface tension state (not morethan 10 in terms of contact angle with water) (corresponding to FIG. 20(A)).

Next, the composition for a red pattern was bar coated onto the wholearea of the photocatalyst-containing layer. As a result, the compositionfor a red pattern was repelled by the photocatalyst-containing layer inits unexposed areas and selectively deposited only onto exposed areas.Thereafter, the assembly was dried at 60° C. for 3 min and then exposedto light from a mercury lamp to cure the composition for a red pattern.Subsequently, heat treatment was carried out at 150° C. for 30 min toform a red pattern (corresponding to FIG. 20 (B)).

Similarly, a photocatalyst-containing layer was formed onto thephotocatalyst-containing layer with a red pattern formed thereon in thesame manner as in Example B-1. The photocatalyst-containing layer in itsgreen pattern forming region was irradiated with light (corresponding toFIG. 20 (C)), and the composition for a green pattern was coated andselectively deposited only onto exposed areas, followed by curingtreatment and heat treatment to form a green pattern (corresponding toFIG. 20 (D)).

Further, a photocatalyst-containing layer was formed onto thephotocatalyst-containing layer with a green pattern formed thereon inthe same manner as in Example B-1. The photocatalyst-containing layer inits blue pattern forming region was irradiated with light, and thecomposition for a blue pattern was coated and selectively deposited onlyonto exposed areas, followed by curing treatment and heat treatment toform a blue pattern.

Next, a two component thermosetting agent (SS7265, manufactured by JapanSynthetic Rubber Co., Ltd.) was spin coated as a protective layer ontothe colored layer. The coating was cured at 200° C. for 30 min to form aprotective layer. Thus, a color filter of the present invention having aconstruction as shown in FIG. 15 was produced (corresponding to FIG. 20(E)).

Example B-6 Formation of Black Matrix

A photocatalyst-containing layer was formed in the same manner as inExample B-1. The photocatalyst-containing layer in its black matrixforming region was irradiated with light. The black matrix compositionwas coated and selectively deposited onto the exposed areas, followed byheat treatment to form a black matrix (corresponding to FIGS. 21 (A) to(B)).

Formation of Colored Layer

Pigment Red 168, Pigment Green 36, and Pigment Blue 60 were firstprovided as pigments. Each mixture having the following composition wasmilled and dispersed by means of a triple roll mill, centrifuged at12,000 rpm, and then filtered through a 1-μm glass filter. 1% by weightof ammonium dichromate as a crosslinking agent was added to theresultant aqueous colored resin solutions to prepare a coating liquidfor a red pattern, a coating liquid for a green pattern, and a coatingliquid for a blue pattern (photosensitive resin compositions).

(Formulation of Mixtures)

Pigment 1 pt. wt. 10 wt % aqueous solution of polyvinyl alcohol 10 pts.wt. (average degree of polymerization of polyvinyl alcohol 1750, degreeof saponification 88 mol %)

A photocatalyst-containing layer was then formed onto thephotocatalyst-containing layer with a black matrix formed thereon in thesame manner as in Example B-1. The photocatalyst-containing layer wasirradiated with light from a mercury lamp (wavelength 365 nm) at anintensity of 70 mW/cm² for 50 see through a mask for a red pattern tobring exposed areas to a high critical surface tension state (not morethan 10° in terms of contact angle with water) (corresponding to FIG. 21(C)).

Next, the composition for a red pattern was bar coated onto the wholearea of the photocatalyst-containing layer. As a result, the compositionfor a red pattern was repelled by the photocatalyst-containing layer inits unexposed areas and selectively deposited only onto exposed areas.Thereafter, the assembly was dried at 60° C. for 3 min and then exposedto light from a mercury lamp to cure the composition for a red pattern.Subsequently, heat treatment was carried out at 150° C. for 30 min toform a red pattern (corresponding to FIG. 21 (D)).

Similarly, a photocatalyst-containing layer was formed onto thephotocatalyst-containing layer with a red pattern formed thereon in thesame manner as in Example B-1. The photocatalyst-containing layer in itsgreen pattern forming region was irradiated with light, and thecomposition for a green pattern was coated and selectively depositedonly onto exposed areas, followed by curing treatment and heat treatmentto form a green pattern. Further, a photocatalyst-containing layer wasformed onto the photocatalyst-containing layer with a green patternformed thereon in the same manner as in Example B-1. Thephotocatalyst-containing layer in its blue pattern forming region wasirradiated with light, and the composition for a blue pattern was coatedand selectively deposited only onto exposed areas, followed by curingtreatment and heat treatment to form a blue pattern.

Next, a two component thermosetting agent (SS7265, manufactured by JapanSynthetic Rubber Co., Ltd.) was spin coated as a protective layer ontothe colored layer. The coating was cured at 200° C. for 30 min to form aprotective layer. Thus, a color filter of the present invention having aconstruction as shown in FIG. 16 was produced (corresponding to FIG. 21(E)).

Example B-7 Formation of Black Matrix

A photocatalyst-containing layer was first formed in the same manner asin Example B-1. The photocatalyst-containing layer in its black matrixforming region was irradiated with light. The black matrix compositionwas coated and selectively deposited onto the exposed areas, followed byheat treatment to form a black matrix.

Formation of Colored Layer

A photocatalyst-containing layer was formed onto thephotocatalyst-containing layer with a black matrix formed thereon in thesame manner as in Example B-1. The photocatalyst-containing layer thusformed was then irradiated with light from a mercury lamp (wavelength365 nm) at an intensity of 70 mW/cm² for 90 sec through a mask having anopening portion (rectangular opening having a size of 23 μm×12 μm) tobring exposed areas to a high critical surface tension state (not morethan 10° in terms of contact angle with water).

A thin layer of a perylene pigment having a chemical structurerepresented by formula B-2 was vacuum deposited onto thephotocatalyst-containing layer under conditions of degree of vacuum1×10⁻⁵ Torr and deposition rate 10 Å/sec to form a thin layer of a redpigment on the whole area of the photocatalyst-containing layer.

The surface of the thin layer of a red pigment was washed with acetone.As a result, the thin layer of the red pigment was separated only fromthe unexposed areas due to the difference between the adhesion of thered pigment to the exposed areas and the adhesion of the red pigment tothe unexposed areas in the photocatalyst-containing layer. Thus, arectangular (23 μm×12 μm) red pattern constituted by a thin layer (layerthickness 0.4 μm) of a red pigment could be formed on the exposed areas.

Example B-8 Formation of Black Matrix

A photocatalyst-containing layer was first formed in the same manner asin Example B-1. The photocatalyst-containing layer in its black matrixforming region was irradiated with light. The black matrix compositionwas coated and selectively deposited onto the exposed areas, followed byheat treatment to form a black matrix.

Formation of Colored Layer

A photocatalyst-containing layer was formed onto thephotocatalyst-containing layer with a black matrix formed thereon in thesame manner as in Example B-1. The photocatalyst-containing layer thusformed was then irradiated with light from a mercury lamp (wavelength365 nm) at an intensity of 70 mW/cm² for 90 sec through a mask having anopening portion (rectangular opening having a size of 23 μm×12 μm) tobring exposed areas to a high critical surface tension state (not morethan 10° in terms of contact angle with water).

A thin layer of a perylene pigment having a chemical structurerepresented by formula B-3 was vacuum deposited onto thephotocatalyst-containing layer under conditions of degree of vacuum1×10⁻⁵ Torr and deposition rate 10 Å/sec to form a thin layer of a bluepigment on the whole area of the photocatalyst-containing layer.

The surface of the thin layer of a blue pigment was washed withmethanol. As a result, the thin layer of the blue pigment was separatedonly from the unexposed areas due to the difference between the adhesionof the blue pigment to the exposed areas and the adhesion of the bluepigment to the unexposed areas in the photocatalyst-containing layer.Thus, a rectangular (23 μm×12 μm) blue pattern constituted by a thinlayer (layer thickness 0.4 μm) of a blue pigment could be formed on theexposed areas.

The following examples demonstrate use of an organic polymer resin layeras the wettability-variable component layer.

Example B-9 Formation of Organic Polymer-containing Layer

Polycarbonate (Iupilon Z400, manufactured by Mitsubishi Gas ChemicalCo., Ltd.) was dissolved in a 3:2 mixed liquid of dichloromethane and1,1,2-trichloroethane to prepare a polycarbonate solution having a solidcontent of 10% by weight.

The polycarbonate solution was then coated onto a transparent substrateprovided with a black matrix of a thin layer pattern of chromium havingan opening size of 140 μm×260 μm and a line width of 30 μm to athickness of 100 μm. The coating was leveled for 15 min and dried at 80°C. for 120 min to form an organic polymer resin layer as awettability-variable component layer. The contact angle of the organicpolymer resin layer with water was measured in the same manner as inExample B-1 and found to be 85° C.

Formation of Colored Layer

Next, a photomask having a light shielding pattern (pattern pitch 155μm×275 μm) with the line width (20 μm) being smaller than the line width(30 μm) of the black matrix was registered with the black matrix throughan organic polymer resin layer, and the organic polymer resin layer wasexposed to light from an excimer lamp (an excimer lamp 172, exposurewavelength 172 mm, manufactured by Heleus) at an output of 90 W for 10sec through this photomask to create surface roughening. Thus, exposedareas were brought to a high critical surface tension (not more than 20°in terms of contact angle with water).

Each of the exposed areas (high critical surface tension areas) had asize of 150 μm×270 μm, and the unexposed areas existed in a width of 20μm on the black matrix.

Pigment Red 168, Pigment Green 36, and Pigment Blue 60 were thenprovided as pigments. Coating liquids for respective color patterns wereprepared using these pigments according to the same formulation as usedin Example B-4.

Subsequently, the composition for a red pattern was dropped as dotshaving a diameter of 90 μm on the center portion of each red patternforming region surrounded by the black matrix through a nozzle.Similarly, the composition for a green pattern was dropped as dotshaving a diameter of 90 μm on the center portion of each green patternforming region surrounded by the black matrix through a nozzle. Further,the composition for a blue pattern was dropped as dots having a diameterof 90 μm on the center portion of each blue pattern forming regionsurrounded by the black matrix through a nozzle. The compositions forrespective color patterns, which had been dropped, were repelled byunexposed areas on the black matrix and homogeneously diffused in andselectively deposited in respective color pattern forming regions havinghigh critical surface tension surrounded by the black matrix.Thereafter, the assembly was heat treated at 100° C. for 45 min. Thus, acolored layer comprising a red pattern, a green pattern, and a bluepattern was formed.

A two component thermosetting agent (SS7265, manufactured by JapanSynthetic Rubber Co., Ltd.) was then spin coated as a protective layeronto the colored layer. The coating was cured at 200° C. for 30 min toform a protective layer. Thus, a color filter of the present inventionhaving a construction as shown in FIG. 14 was produced.

(Evaluation)

The color filters prepared in Examples B-1 to B-9 were observed under anoptical microscope. As a result, the black matrix and the colored layerwere fi-ee from discoloration, color mixing, dropouts, and uneven colorand other defects.

As is apparent from the foregoing detailed description, according to thesecond invention B, the wettability by the composition for a lightshielding layer and the composition for a colored layer is higher inareas having specific wettability, and, upon supply of the compositionfor a light shielding layer and the composition for a colored layer, thecomposition for a light shielding layer and the composition for acolored layer are selectively and surely deposited only onto the areashaving specific wettability, while they are repelled by the other areas.This makes it possible to form a light shielding layer and a coloredlayer with high accuracy, which in turn can realize the provision ofhigh resolution color filters. Further, the coating compositions areselectively deposited only onto areas where the light shielding layerand the colored layer are to be formed. Therefore, the materials can beefficiently used, and the step of development and washing and the stepof treating waste water are unnecessary. This simplifies the process.Further, using a photocatalyst-containing layer or an organic polymerresin layer as the wettability-variable component layer for specificwettability areas enhances the critical surface tension of exposed areasthrough photocatalytic action to bring the exposed areas to a highcritical surface tension state (to form areas having specificwettability), or roughens the surface through a reduction in molecularweight as a result of cleavage of a polymer chain to bring the exposedareas to a high critical surface tension (to form areas having specificwettability), while the low critical surface tension of the unexposedareas remained unchanged. Upon supply of the composition for a lightshielding layer and the composition for a colored layer onto thephotocatalyst-containing layer or the organic polymer resin layer, thecomposition for a light shielding layer and the composition for acolored layer are repelled by the unexposed areas and are selectivelyand surely deposited only onto the exposed areas having high wettability(high critical surface tension areas).

Example C-1 (Photocatalyst-containing Layer) (For Waterless Printing)

3 g of isopropyl alcohol, 0.4 g of an organosilane (TSL8113,manufactured by Toshiba Silicone Co., Ltd.), 0.3 g of afluoroalkylsilane (MF-160E, manufactured by Tohchem ProductsCorporation), and 2 g of an inorganic coating composition for aphotocatalyst (ST-K01, manufactured by Ishihara Sangyo Kaisha Ltd.).This composition for a photocatalyst-containing layer was spin coatedonto a transparent substrate of quartz glass. The coating was dried at atemperature of 150° C. for 10 min, permitting hydrolysis andpolycondensation to proceed. Thus, a transparentphotocatalyst-containing layer (thickness 0.2 μM) with a photocatalystbeing strongly fixed in an organopolysiloxane was formed. Thephotocatalyst-containing layer was pattern-wise exposed to light from amercury lamp at an intensity of 70 mW/cm² through a mask for 50 sec. Thecontact angle of exposed areas and unexposed areas with water wasmeasured with a contact angle goniometer (Model CA-Z, manufactured byKyowa Interface Science Co., Ltd.). As a result, the contact angle ofthe unexposed areas with water was 142°, while the contact angle of theexposed areas with water was not more than 10° Thus, a pattern wasformed by utilizing a difference in wettability between the exposedareas and the unexposed areas.

Example C-2 (Microlens) (Waterless) (Coating)

The photocatalyst-containing layer described in Example C-1 was spincoated onto a transparent substrate of quartz glass. The coating wasexposed at an intensity of 70 mW/cm² from a mercury lamp for 90 seethrough a negative-working photomask having a circular pattern withseveral openings having a diameter of 50 μm being arranged at intervalsof 2 μm in to prepare a transparent substrate having thereon a circularpattern having high wettability. 1000 g of a water-soluble WV curableresin (AQ-9, ester acrylate resin, manufactured by Arakawa ChemicalIndustries, Ltd.), 50 g of a curing initiator (Irgacure 1173,manufactured by Ciba Specialty Chemicals, K.K.), and 125 g of distilledwater (manufactured by Junsei Chemical Corporation) were mixed together,and the mixture was stirred for 3 min. The mixed liquid was coated bybead coating (slide coating) onto the transparent substrate havingthereon a circular pattern utilizing a difference in wettability to athickness of 12 μm. As a result, the mixed liquid was selectivelydeposited onto the exposed areas (circular pattern areas). The assemblywas then exposed at an intensity of 70 mW/cm² from a mercury lamp for 5see to prepare an array of microlenses having a diameter of 50 μm and afocal length of 1 mm.

Example C-3 (Microlens) (Waterless) (Ejection)

The photocatalyst-containing layer described in Example C-1 was spincoated onto a transparent substrate of quartz glass. The coating wasexposed at an intensity of 70 mW/cm² from a mercury lamp for 90 secthrough a negative-working photomask having a circular pattern with aplurality of openings having a diameter of 200 μm being arranged atintervals of 100 μm. Thus, a transparent substrate having thereon acircular pattern having high wettability was prepared.

1000 g of a water-soluble UV curable resin (AQ-11, ester acrylate resin,manufactured by Arakawa Chemical Industries, Ltd.), 50 g of a curinginitiator (Irgacure 184, manufactured by Ciba Specialty Chemicals,K.K.), and 25 g of distilled water (manufactured by Junsei ChemicalCorporation) were mixed together, and the mixture was stirred for 3 min.The mixed liquid was ejected in an amount of 0.0001 ml on the center ofthe circular pattern portion on the transparent substrate having acircular pattern utilizing a difference in wettability by a liquidprecision constant rate ejection apparatus (Dispenser 1500XL-15,manufactured by EFD). As a result, the ejected liquid was spread onlyonto the circular pattern portion without spreading onto the otherareas. The assembly was then exposed at an intensity of 70 mW/cm² from amercury lamp for 10 sec to prepare an array of microlenses having adiameter of 200 μm and a focal length of 500 μm.

Example C-4 (Photocatalyst-containing Layer) (Dampening Water)

3 g of isopropyl alcohol, 4.2 g of an organosilane (TSL8113,manufactured by Toshiba Silicone Co., Ltd.), and 0.2 g of a titaniumoxide powder (ST-01, average particle diameter 7 nm, manufactured byIshihara Sangyo Kaisha Ltd.) were mixed together. The mixture wasstirred for 20 min while maintaining the temperature at 100° C. Theresultant dispersion was spin coated onto a transparent substrate ofquartz-glass. The coating was dried at a temperature of 150° C. for 10min, permitting hydrolysis and polycondensation to proceed. Thus, a 0.2μm-thick layer was formed. The layer was irradiated with ultravioletlight from a higher pressure mercury lamp at an intensity of 70 mW/cm²for 50 sec. The contact angle of the sample with water and n-octane wasmeasured with a contact angle goniometer (Model CA-Z, manufactured byKyowa Interface Science Co., Ltd.). As a result, before the irradiation,the contact angle was 72° for water and not more than 5° for n-octane,while after the irradiation, the contact angle was 0° for water and notmore than 5° for n-octane.

Example C-5 (Microlens) (Dampening Water) (Ejection)

The photocatalyst-containing layer described in Example C-4 was spincoated onto a transparent substrate of quartz glass. The coating wasexposed at an intensity of 70 mW/cm² from a mercury lamp for 90 secthrough a positive-working photomask having a square pattern with aplurality of openings having a size of 200 μm×200 μm being arranged atintervals of 100 μm. Thus, a transparent substrate having thereon asquare pattern utilizing a difference in wettability was prepared. Asolution (dampening water) prepared by mixing 10 g of a clean etchliquid manufactured by Nikken Chemicals Co., Ltd. and 190 g of distilledwater (manufactured by Junsei Chemical Corporation) together was spincoated onto the transparent substrate having a square pattern utilizinga difference in wettability. As a result, the mixed liquid was coatedonly onto exposed areas (areas other than the square pattern).

1000 g of UV curable resin (Beam Set 267, acrylic resin, manufactured byArakawa Chemical Industries, Ltd.) and 50 g of a curing initiator(Irgacure 184, manufactured by Ciba Specialty Chemicals, K.K.) weremixed together, and the mixture was stirred for 3 min. The mixed liquidwas ejected in an amount of 0.0001 ml on the center of the squarepattern portion not coated with the clean etch liquid in the transparentsubstrate by a liquid precision constant rate ejection apparatus(Dispenser 1500XL-15, manufactured by EFD). As a result, the ejectedliquid was spread only onto the square pattern portion without spreadingonto the other areas. The assembly was then exposed at an intensity of70 mW/cm² from a mercury lamp for 10 sec to prepare an array ofmicrolenses having a square bottom of 200 μm×200 μm and a focal lengthof 500 μm.

Example C-6 (Colored microlens) (Waterless) (Ejection)

The photocatalyst-containing layer described in Example C-1 was spincoated onto a transparent substrate of quartz glass. The coating wasexposed at an intensity of 70 mW/cm² from a mercury lamp for 90 secthrough a negative-working photomask having a circular pattern with aplurality of openings having a diameter of 200 μm being arranged atintervals of 100 μm. Thus, a transparent substrate having thereon acircular pattern having high wettability was prepared.

10 g of a water-soluble UV curable resin (AQ-11, ester acrylate resin,manufactured by Arakawa Chemical Industries, Ltd.), 0.5 g of a curinginitiator (Irgacure 184, manufactured by Ciba Specialty Chemicals,K.K.), 1.25 g of distilled water, and 0.5 g of a red dye (Rose Bengal,manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed together.The mixture was stirred for 3 min to prepare a composition for a redlens.

10 g of a water-soluble UV curable resin (AQ-11, ester acrylate resin,manufactured by Arakawa Chemical Industries, Ltd.), 0.5 g of a curinginitiator (Irgacure 184, manufactured by Ciba Specialty Chemicals,K.K.), 1.25 g of distilled water, and 0.5 g of a green dye (BrilliantGreen, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixedtogether. The mixture was stirred for 3 min to prepare a composition fora green lens.

10 g of a water-soluble UV curable resin (AQ-11, ester acrylate resin,manufactured by Arakawa Chemical Industries, Ltd.), 0.5 g of a curinginitiator (Irgacure 184, manufactured by Ciba Specialty Chemicals,K.K.), 1.25 g of distilled water, and 0.5 g of a blue dye (VictoriaBlue, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixedtogether. The mixture was stirred for 3 min to prepare a composition fora blue lens.

The compositions for lenses were ejected in an amount of 0.0001 ml onthe center of the circular pattern portion, specified for red, green,and blue, on the transparent substrate having a circular patternutilizing a difference in wettability by a liquid precision constantrate ejection apparatus (Dispenser 1500XL-15, manufactured by EED). As aresult, the ejected liquid was spread only onto the circular patternportion without spreading onto the other areas. The assembly was thenexposed at an intensity of 70 mW/cm² from a mercury lamp for 10 sec toprepare an array of colored microlenses having a diameter of 200 μm anda focal length of 500 μm.

Example C-7 (Colored microlens) (Waterless) (Coating)

The photocatalyst-containing layer described in Example C-1 was spincoated onto a transparent substrate of quartz glass. The coating wasexposed at an intensity of 70 mW/cm² from a mercury lamp for 90 seethrough a negative-working photomask having a circular pattern with aplurality of openings having a diameter of 200 μm being arranged atintervals of 100 μm in the longitudinal direction and at intervals of700 μm in the lateral direction. Thus, a transparent substrate havingthereon a circular pattern having high wettability was prepared.

10 g of a water-soluble UV curable resin (AQ-9, ester acrylate resin,manufactured by Arakawa Chemical Industries, Ltd.), 0.5 g of a curinginitiator (Irgacure 1173, manufactured by Ciba Specialty Chemicals,K.K.), 1.25 g of distilled water, and 0.5 g of a red dye (Rose Bengal,manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed together.The mixture was stirred for 3 min to prepare a composition for a redlens.

10 g of a water-soluble UV curable resin (AQ-9, ester acrylate resin,manufactured by Arakawa Chemical Industries, Ltd.), 0.5 g of a curinginitiator (Irgacure 1173, manufactured by Ciba Specialty Chemicals,K.K.), 1.25 g of distilled water, and 0.5 g of a green dye (BrilliantGreen, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixedtogether. The mixture was stirred for 3 min to prepare a composition fora green lens.

10 g of a water-soluble UV curable resin (AQ-9, ester acrylate resin,manufactured by Arakawa Chemical Industries, Ltd.), 0.5 g of a curinginitiator (Irgacure 1173, manufactured by Ciba Specialty Chemicals,K.K.), 1.25 g of distilled water, and 0.5 g of a blue dye (VictoriaBlue, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixedtogether. The mixture was stirred for 3 min to prepare a composition fora blue lens.

The composition for a red lens was dip coated onto a transparentsubstrate having thereon a circular pattern utilizing a difference inwettability to a thickness of 12 μm. As a result, the mixed liquid wasdeposited only onto the exposed areas (circular pattern areas). Theassembly was exposed to light from a mercury lamp at an intensity of 70mW/cm² for 10 sec to cure the coating.

A photocatalyst-containing layer was formed on the substrate havingthereon a red lens in the same manner as described above. A circularpattern having high wettability was formed while leaving a space of 100μm from the longitudinal column of the red lens in the same manner asdescribed above. A green lens was formed in the same manner as describedabove in connection with the formation of the red lens, except that thecomposition for a green lens was used.

The above procedure was repeated, except that a composition for a bluelens was used. As a result, a blue lens was formed between thelongitudinal columns of red and green while leaving a space of 100 μmfrom the longitudinal columns of red and green. Thus, an array of colormicrolenses having a diameter of 200 μm and a focal length of 1 mm.

Example C-8 (Light Shielding Layer) (Waterless) (Coating)

The photocatalyst-containing layer described in Example C-1 was formedon the backside of the quartz glass as the substrate for an array ofmicrolenses having a diameter of 100 μm and arranged at intervals of 10μm. Next, a photomask with openings having a diameter of 10 μm andarranged at intervals of 100 μm was registered with the lenses, followedby pattern-wise exposure to light from a mercury lamp.

4 g of carbon black (#950, Mitsubishi Chemical Corporation), 0.7 g ofpolyvinyl alcohol (Gosenol AH-26, Nippon Synthetic Chemical IndustryCo., Ltd.), and 95.3 g of ion-exchanged water were mixed together whileheating at 90° C. to prepare a solution which was then centrifuged at12000 rpm and filtered through a 1-μm glass filter to prepare acomposition for a light shielding layer. The composition for a lightshielding layer was blade coated onto the whole area of the exposedphotocatalyst-containing layer. As a result, the composition wasrepelled by unexposed areas and selectively deposited only onto exposedareas. The coating was then heated at 150° C. for 30 min to form a lightshielding layer.

Example C-9 (Light Shielding Layer) (Waterless) (Ejection)

The photocatalyst-containing layer described in Example C-1 was formedon the backside of the quartz glass as the substrate for an array ofmicrolenses having a diameter of 700 μm and arranged at intervals of 10μm. Next, a photomask with openings having a diameter of 10 μm andarranged at intervals of 700 μm was registered with the lenses, followedby pattern-wise exposure to light from a mercury lamp.

Next, the composition for a light shielding layer described in ExampleC-8 was ejected by means of a dispenser (manufactured by EFD) onto theexposed areas to deposit the composition for a light shielding layeronly onto exposed areas. The assembly was then heated at 150° C. for 30min to form a light shielding layer.

Example C-10 (Light Shielding Layer) (Dampening water) (Coating)

The photocatalyst-containing layer described in Example C-4 was formedon the backside of the quartz glass as the substrate for an array ofmicrolenses having a diameter of 100 μm and arranged at intervals of 10μm. Next, a photomask with light shielding areas having a diameter of 10μm and arranged at intervals of 100 μm was registered with the lenses,followed by pattern-wise exposure to light from a mercury lamp.

Dampening water (a liquid prepared by diluting a clean etch liquid 20times with water, manufactured by Nikken Chemicals Co., Ltd.) was bladecoated onto the whole area. As a result, the dampening water selectivelywet only exposed areas.

A printing ink (ACROS(EIKUROSU) Black, manufactured by The Inctec Inc.)was roll coated at 30 rpm onto the whole area. As a result, the ink wasselectively deposited only onto unexposed areas. The coating was heatedat 100° C. for 3 min to remove the dampening water. Thus, a lightshielding layer was formed.

Example C-11 (Light Shielding Layer) (Dampening Water) (Ejection)

The photocatalyst-containing layer described in Example C-4 was formedon the backside of the quartz glass as the substrate for an array ofmicrolenses having a diameter of 700 μm and arranged at intervals of 10μm. Next, a photomask with light shielding areas having a diameter of 10μm and arranged at intervals of 700 μm was registered with the lenses,followed by pattern-wise exposure to light from a mercury lamp.

Dampening water (a liquid prepared by diluting a clean etch liquid 20times with water, manufactured by Nikken Chemicals Co., Ltd.) was bladecoated onto the whole area. As a result, the dampening water selectivelywet only exposed areas.

A solution prepared by diluting a printing ink (ACROS (EIKUROSU) Black,manufactured by The Inctec Inc.) three times with n-hexadecane wasejected by means of a dispenser (manufactured by EFD) onto unexposedareas to deposit the printing ink only onto the unexposed areas. Theassembly was then heated at 100° C. for 30 min to remove the dampeningwater. Thus, a light shielding layer was formed.

Example C-12 (Microlens) (Ejection) (Variation in Focal Length byVarying Amount of Ejection: Comparative Example)

The photocatalyst-containing layer described in Example C-1 was spincoated onto a transparent substrate of quartz glass. The coating wasexposed at an intensity of 70 mW/cm² from a mercury lamp for 90 seethrough a mask having a circular pattern with the diameter of theopening being 9 mm. Thus, a transparent substrate having thereon acircular pattern having high wettability was prepared.

1000 g of a water-soluble WV curable resin (AQ-7, ester acrylate resin,manufactured by Arakawa Chemical Industries, Ltd.), 50 g of a curinginitiator (Irgacure 184, manufactured by Ciba Specialty Chemicals,K.K.), and 25 g of distilled water (manufactured by Junsei ChemicalCorporation) were mixed together. The mixture was stirred for 3 min. Themixed liquid was ejected in an amount of 15 to 55 μL through amicrosyringe onto the center of the circular pattern portion on thetransparent substrate having thereon the circular pattern utilizing adifference in wettability. As a result, the ejected liquid was spreadonly onto the circular pattern portion and was not spread onto the otherareas. The larger the amount of the liquid dropped, the larger thecontact angle with the substrate. The assembly was exposed to light froma mercury lamp at an intensity of 70 mW/cm² for 10 sec to cure thecoating. Thus, lenses having a diameter of 9 mm and a focal length of 27to 90 mm could be designed and prepared by varying the amount of theresin mixed liquid ejected.

For comparison, the resin mixed liquid was ejected in an amount of 15 to55 μL onto a transparent substrate of quartz glass not having aphotocatalyst-containing layer (a substrate not having a wettablepattern). In this case, ejection of the liquid in a larger amountresulted in wetting in a larger area and unstable shape in wetted area,that is, various shapes in wetted area. Further, the contact angle ofthe liquid with the substrate remained unchanged when the amount of theliquid ejected was increased. The assembly was exposed to light from amercury lamp at an intensity of 70 mW/cm² for 10 sec. The lenses thusobtained had uncontrolled shape, diameter, and focal length. The contactangle of the liquid with the substrate and the diameter and focal lengthof the resultant lenses as a function of the amount of the resinsolution (composition for a lens) ejected are shown in the followingtable.

Among of resin mixed Contact angle of Radius Focal length liquid droppedliquid with substrate of lens of lens (μL) (°) (mm) (mm) Substrate witha wettable pattern formed thereon 15.0 12.4 9.0 90.4 20.0 16.3 9.0 52.030.0 19.5 9.0 46.3 40.0 22.6 9.0 40.3 50.0 33.4 9.0 31.2 55.0 38.4 9.027.8 Substrate with a wettable pattern not formed thereon 15.0 18.9 8.070.0 20.0 22.6 7.0 68.3 30.0 18.4 9.0 70.5 40.0 24.1 10.0 66.5 50.0 22.611.0 68.0 55.0 22.6 12.0 68.0

According to the third invention C, there is provided a process forsimply producing a lens that, particularly in the production ofmicrolenses and an array of microlenses, can provide high positionalaccuracy and shape accuracy and can produce microlenses, and facilitatesthe regulation of the local length. Further, a simple process forforming a light shielding layer of lenses can be also provided.

Example D-1

3 g of isopropyl alcohol, 0.4 g of an organosilane (TSL8113,manufactured by Toshiba Silicone Co., Ltd.), 0.15 g of afluoroalkylsilane (MF-160E, manufactured by Tohchem ProductsCorporation), and 2 g of a titanium oxide coating composition for aphotocatalyst (ST-K01, manufactured by Ishihara Sangyo Kaisha Ltd.) weremixed together. The resultant dispersion was stirred for 20 min whilemaintaining the temperature at 100° C. to prepare a composition for aphotocatalyst-containing layer. The composition was spin coated onto a0.15 mm-thick polyester film. The coated polyester was dried at 130° C.for 10 min, permitting hydrolysis and polycondensation to proceed. Thus,a photocatalyst-containing layer with a photocatalyst being stronglyfixed in an organopolysiloxane was obtained.

The photocatalyst layer was exposed to light from a mercury lamp(HI-40N, manufactured by Japan Storage Battery Co., Ltd.) at anintensity of 70 mW/cm² (365 nm) for 50 sec through a gradationnegative-working mask having halftone dots of 2 to 98% with 175lines/in.

After the exposure, the contact angle of the photocatalyst-containinglayer with water was not more than 5° for exposed areas and 107° forunexposed areas.

Next, the following silicone rubber composition was roll coated at 400m/min onto the exposed photocatalyst-containing layer.

(1) Polydimethylsiloxane having silanol on   86 g its both ends (numberaverage molecular weight 100,000) (2) Ethyltriacetoxysilane 13.9 g (3)Dibutyltin diacetate  0.1 g (4) Toluene  300 g

As a result, the silicone rubber composition could be coated only ontothe photoreceptive areas, that is, the wettability-varied areas. Theassembly was dried at 120° C. for 2 min to form a pattern of a 1.5μm-thick silicone rubber layer. Next, under the same conditions, thewhole area exposure was carried out using a mercury lamp to vary thewettability of the areas not provided with the silicone rubber layer.The printing plate thus obtained was mounted on an offset printingmachine (Alpha New Ace, manufactured by Alpha Giken K.K.), and printingwas carried out on a coated paper using a printing ink (Inctec WaterlessS Deep Blue, manufactured by The Inctec Inc.) at a printing speed of5000 sheets/hr. As a result, 20,000 sheets of good prints could beobtained.

Example D-2

The photocatalyst-containing layer described in Example D-1 was formedon a 0.15 mm-thick aluminum sheet in the same manner as in Example D-1.The photocatalyst-containing layer was then exposed to light from amercury lamp through a gradation negative-working mask having halftonedots of 2 to 98% with 175 lines/in in the same manner as in Example D-1.The following O/W type emulsion type silicone composition was rollcoated at 450 m/min onto the exposed photocatalyst-containing layer.

(1) Polydimethylsiloxane having hydroxyl group 95 g  on its both ends(number average molecular weight 100,000) (2) Methyltriacetoxysilane 5 g(3) Dibutyltin dilaurate 0.01 g   (4) Dodecylbenzenesulfonic acid 5 g

As a result, the composition was coated only onto the exposed areas,that is, the wettability-varied areas. The assembly was dried at 120° C.for 10 mm to form a pattern of a 1.5 μm-thick silicone rubber layer.Next, under the same conditions, the whole area exposure was carried outusing a mercury lamp to vary the wettability of the areas not providedwith the silicone rubber layer.

The printing plate thus obtained was mounted on an offset printingmachine (Alpha New Ace, manufactured by Alpha Giken K. K.), and printingwas carried out on a coated paper using a printing ink (Inctec WaterlessS Deep Blue, manufactured by The Inctec Inc.) at a printing speed of5000 sheets/hr. As a result, 20,000 sheets of good prints could beobtained.

Example D-3

The photocatalyst-containing layer described in Example D-1 was formedon a 0.15 mm-thick polyester film in the same manner as in Example D-1.The photocatalyst layer was then exposed to light from a mercury lampthrough a gradation negative-working mask having halftone dots of 2 to98% with 175 lines/in in the same manner as in Example D-1. Thefollowing silicone rubber composition was roll coated at 400 m/min ontothe exposed photocatalyst-containing layer.

(1) Polydimethylsiloxane having vinyl group 100 g on its both ends (2)(CH₃)SiO(Si(CH₃)₂O)₃₀(SiH(CH₃)O)₁₀Si(CH₃) 312.8 g   (3) Chloroplatinicacid/methyl vinyl cyclic complex  0.1 g (4) Toluene 200 g

As a result, the silicone rubber composition was coated only onto theexposed areas, that is, the wettability-varied areas. The assembly wasdried at 120° C. for 5 min to form a 1.5 μm-thick patterned siliconerubber layer. Next, under the same conditions, the whole area exposurewas carried out using a mercury lamp to vary the wettability of theareas not provided with the silicone rubber layer.

The printing plate thus obtained was mounted on an offset printingmachine (Alpha New Ace, manufactured by Alpha Giken K.K.), and printingwas carried out on a coated paper using a printing ink (Inctec WaterlessS Yellow, manufactured by The Inctec Inc.) at a printing speed of 5000sheets/hr. As a result, 20,000 sheets of good prints could be obtained.

Example D-4

The photocatalyst-containing layer described in Example D-1 was formedon a 0.15 mm-thick aluminum substrate in the same manner as in ExampleD-1. The photocatalyst layer was then exposed to light from a mercurylamp through a gradation negative-working mask having halftone dots of 2to 98% with 175 lines/in in the same manner as in Example D-1.

The following composition was roll coated at 520 m/min onto the exposedphotocatalyst-containing layer.

(1) KAYARAD D-310, manufactured by Nippon 18 g Kayaku Co., Ltd.) (2)Darocur 1173, manufactured by Ciba-Geigy 0.9 g  Limited) (3) Xylene 20 g

As a result, the composition was coated only onto the exposed areas,that is, the wettability-varied areas. The assembly was then irradiatedwith ultraviolet light from a mercury lamp at an intensity of 70 mW/cm²for 50 sec to cure the composition and, at the same time, to vary thewettability of the areas not wetted by the composition. Thus, a printingplate was obtained which had a surface having an enhanced criticalsurface tension of not more than 10° in terms of contact angle thereofwith water.

The printing plate thus obtained was mounted on an offset printingmachine (Alpha New Ace, manufactured by Alpha Giken K.K.), and printingwas carried out on coated paper using a printing ink (ACROS(EIKUROSU)Deep Red, manufactured by The Inctec Inc.) and dampening water (a liquidprepared by diluting a clean etch liquid 20 times with water,manufactured by Nikken Chemicals Co., Ltd.) at a printing speed of 5000sheets/hr. As a result, 20,000 sheets of good prints could be obtained.

Thus, according to the plate for lithography of the fourth invention D,a photocatalyst-containing composition layer is formed on a substrate,the wettability of the surface is varied by photocatalytic actioncreated in response to light irradiation, and a resin layer is coated,followed by the whole area exposure to form areas having enhancedcritical surface tension in areas other than the resin layer. This canrealize the production of plates for waterless lithography orlithography using dampening water that possesses high plate wear.

1. A method for pattern formation adapted for optically forming apattern, wherein a structure for pattern formation, exposedpattern-wise, comprising: a substrate; a photocatalyst-containing layerprovided on the substrate; and, provided on the photocatalyst-containinglayer; a layer that is decomposable and removable through photocatalyticaction upon pattern-wise exposure, and the wettability of the surface ischanged by the action of the photocatalyst.
 2. The method for patternformation according to claim 1, wherein the pattern-wise exposure of thephotocatalyst-containing layer is carried out by light beam exposure. 3.The method for pattern formation according to claim 1, wherein thepattern-wise exposure of the photocatalyst-containing layer is carriedout by exposure through a photomask.
 4. The method for pattern formationaccording to claim 1, wherein the pattern-wise exposure of thephotocatalyst-containing layer is carried out while heating thestructure for pattern formation.
 5. A process for producing an element,comprising the steps of: providing a structure for pattern formationcomprising: a substrate; a photocatalyst-containing layer provided onthe substrate; and, provided on the photocatalyst-containing layer, alayer that is decomposable and removable through photocatalytic actionupon pattern-wise exposure, and forming a functional layer provided onthe structure for pattern formation in areas corresponding to a pattern,of the structure for pattern formation, obtained by the pattern-wiseexposure, wherein the wettability of the surface is changed by theaction of the photocatalyst.
 6. The process for producing an elementaccording to claim 5, wherein the functional layer is formed on thestructure for pattern formation by ejecting a composition for afunctional layer through a nozzle.
 7. The process for producing anelement according to claim 6, wherein the ink-jet system is used for thenozzle ejection.
 8. The process for producing an element according toclaim 5, comprising the steps of: adhesion of a composition for afunctional layer onto the whole surface of the structure for patternformation, and forming the functional layer by transferring thecomposition for a functional layer in pattern-wise only to the exposedwettability-varied area, due to a difference in adherence of a layerthat is decomposable and removable through photocatalytic action uponpattern-wise exposure and a photocatalyst-containing layer, on anothersubstrate.
 9. The process for producing an element according to claim 5,wherein the functional layer is formed on the structure for patternformation by thermal or pressure transfer from a film coated with acomposition for a functional layer or a roll coated with a compositionfor a functional layer.
 10. The process for producing an elementaccording to claim 5, wherein the functional layer is formed on thestructure for pattern formation by film formation utilizing electrolessplating.
 11. The process for producing an element according to claim 5,comprising the steps of: laminating a composition for a functional layeronto the whole surface of the structure for pattern formation, andremoving the functional layer, provided on a layer that is decomposableand removable through photocatalytic action upon pattern-wise exposure,in its unexposed areas, to form a patterned functional layer.
 12. Theprocess for producing an element according to claim 11, wherein thefunctional layer is formed on the structure for pattern formation bycoating a composition for a functional layer.
 13. The process forproducing an element according to claim 11, wherein the functional layeris formed on the structure for pattern formation by film formation of acomposition for a functional layer, utilizing vacuum.
 14. The processfor producing an element according to claim 11, wherein the functionallayer is formed on the structure for pattern formation by transferring acomposition for a functional layer.
 15. The process for producing anelement according to claim 11, wherein the functional layer is formed onthe structure for pattern formation by ejecting a composition for afunctional layer through a nozzle.
 16. The process for producing anelement according to claim 15, wherein the ejecting through a nozzle isdone by an ink-jet system.
 17. The process for producing an elementaccording to claim 11, wherein the functional layer, provided on a layerthat is decomposable and removable through photocatalytic action uponpattern-wise exposure, in its unexposed areas, is removed by a solvent.18. The process for producing an element according to claim 11, whereinthe functional layer, provided on a layer that is decomposable andremovable though photocatalytic action upon pattern-wise exposure, inits unexposed areas, is removed by adhering and peeling off a substratewhich adhesive layer is formed.